Process for the preparation of butenoyl norbornenes

ABSTRACT

A process is disclosed comprising adding a compound, 2-acetyl-3,3-dimethyl-5-norbornene having the structure: ##STR1## to acetaldehyde according to the reaction sequence: ##STR2## whereby a compound having the structure: ##STR3## is formed useful as an organoleptic.

This application is a divisional of application for U.S. Letters patentSer. No. 765,847, filed on Feb. 4, 1977, now U.S. Pat. No. 4,076,853.

BACKGROUND OF THE INVENTION

The present invention relates to substituted norbornane derivatives ofthe genus of compounds having the structure: ##STR4## wherein each ofthe dashed lines represents a carbon-carbon single bond or acarbon-carbon double bond with the proviso that at least one of thedashed lines is a carbon-carbon single bond; wherein n is 0 or 1 withthe proviso that n is 1 when both dashed lines are carbon-carbon singlebonds and n is 0 when one of the dashed lines is a carbon-carbon doublebond; wherein R₁ and R₂ are each the same or different hydrogen or loweralkyl; wherein Y is: ##STR5## wherein Z is one of the moieties: ##STR6##wherein R₃ and R₄ are each alkyl; wherein R₇, R₈ and R₁₀ are each thesame or different hydrogen or lower alkyl; wherein R₉ and R₉ ^(') takenseparately are the same or different lower alkyl, or taken together islower alkylene; wherein the dotted line represents a carbon-carbonsingle bond or a carbon-carbon double bond; and wherein each of the wavylines represents, in the alternative, exo or endo isomers, produced bythe novel processes of our invention, and to novel compositions usingone or more of such substituted norbornane derivatives to alter, modifyor enhance the flavor and/or aroma of consumable materials or impartflavor and/or aroma to consumable materials.

There has been considerable work performed relating to substances whichcan be used to impart (modify, augment or enhance) flavors andfragrances to (or in) various consumable materials. These substances areused to diminish the use of natural materials, some of which may be inshort supply, and to provide more uniform properties in the finishedproduct.

Fruity, piney/green, winey, fruity-estery, cedarwood, floral, woody,balsam tree resin-like, sweet, fruity berry, incense, minty, balsam,blueberry, piney, green fruity and/or pine needle/green aromas withpiney, eugenol/clove, spicey, fruity, winey, sweet, banana-like, estery,balsam tree resin-like, woody, incense, warm tea-like, floral,cedarwood, rosey, berry, tea, astringent, bitter, camphoraceousgreen/earthy, green, minty, earthy, red beet-like, balsam natural-like,balsam resin-like, rum-like and/or blueberry tastes are particularlydesirable for many uses in foodstuff flavors, chewing gum flavors,toothpaste flavors and medicinal product flavors.

Sweet, woody, fruity, cooling aroma prior to smoking and sweet, naturaltobacco like smoke flavor characteristics in the mainstream on smokingare desirable in tobaccos and in tobacco flavoring compositions.

Intense and pleasant, twiggy, melony, sweet, woody, fruity, spicey(nutmeg, pepper), herbaceous, fir-balsam, thujone-like, cedar leaf,camphoraceous, musty, minty, fresh cut pine/spruce, artemesia,natural-like, cresylic, borneol aromas with strong armoise-likeundertones are desirable in several types of perfume compositions,perfumed articles and colognes.

U.S. Pat. No. 3,852,358 issued on Dec. 3, 1974, discloses a process forproducing 2-acetyl-3,3-dimethyl-5-norbornene in both the exo and endoforms which have uses in perfumery and other fragrance applications.These compounds have the structures: ##STR7## These compounds, producedby reaction of cyclopentadiene with mesityl oxide, are startingmaterials for producing a number of the compounds of our invention.However, the compounds of our invention have unexpected, unobvious andadvantageous properties when compared with the2-acetyl-3,3-dimethyl-5-norbornene of U.S. Pat. No. 3,852,358.

U.S. Pat. No. 3,942,761 discloses the use of perfumery of4-(2'-norbornyl)-2-butanones having the structure: ##STR8## wherein R₁is hydrogen or methyl and R is hydrogen or lower alkyl containing from 1to 8 carbon atoms. Such compounds have structures which are different inkind from the structures of the compounds of our invention. Alsodisclosed as intermediates for producing the foregoing compounds arecompounds having the generic structure: ##STR9## wherein the dotted lineis a carbon-carbon single bond or a carbon-carbon double bond. Inaddition, the following reaction sequence is set forth therein:##STR10##

Arctander, "Perfume and Flavor Chemicals", 1969, Vol. 1, discloses theuse in perfume compositions and in foodstuff flavors of "fenchone","fenchyl alcohol", "camphene carbinol", and "camphene carbinyl acetate",thus:

(i) "1385: FENCHONE

laevo-Fenchone. (dextro- is known but less common as a fragrancematerial).

1,3,3-Trimethyl-2-norbornanone.

1,3,3-Trimethyl bicyclo-1,2,2-heptanone-2. ##STR11## Warm-camphoraceous,powerful and diffusive, basically sweet odor. Warm, somewhat burning andbitter taste with a medicinal note.

This ketone finds some use as a masking odor in industrial fragrances.It is also used in the reconstruction of Fennel oil and a few otheressential oils.

In spite of its rather unpleasant taste, it is used in various Berrycomplex flavors, in Spice complexes and in certain types of Liquerflavoring.

The concentration used is about 0.1 to 5 ppm in the finished product.

(ii) "1387: FENCHYL ALCOHOL

1,3,3-trimethyl-2-norbornanol.

1,3,3-Trimethyl bicyclo-1,2,2-heptanol-2.

2-Fenchanol.

Fenchol. ##STR12## The racemic alpha-Fenchol has a somewhat lowermelting point, and the beta-Fenchols are all liquid at room temperature.

Fenchol made by reduction of Fenchone from Cedarleaf oil is usually amixture of several isomers, including the crystalline alpha-isomers. Thebeta-isomer forms a crystalline Hydrate which may be solid at roomtemperature.

Almost insoluble in water, soluble in alcohol, miscible with oils.Powerful and diffusive, Camphor-like, but sweeter and more Citrus-likealmost Lime-like odor with more or less or an earthy-dry character,according to the composition and isomer-ratio.

The taste is somewhat bitter-Lime-like, camphoraceous and slightlywoody-musty.

This interesting alcohol (or mixed alcohols) finds use in perfumecompositions ranging from woody or herbaceous to Citrus-Lime and evencertain floral types. It produces power and "lift" to floral fragrances,and solid background to Lime and other Citrus bases, having theadvantage over the Terpenes in being very stable in soap.

Fenchyl alcohol is also used in flavor compositions such as Strawberryand other berries, Lime and Spice, etc.

The concentration is normally low, e.g. 0.2 up to 5 ppm in the finishedproduct".

(iii) "1028: 3,3-DIMETHYL-Δ², beta-NORBORNANE-2-ETHANOL "Camphenecarbinol". ##STR13## Sweet-camphoraceous, warm and soft odor with awoody undertone. Upon standing it may develop an odor resembling that ofCelluloid.

Although rarely offered commercially, this chemical could find some usein perfume compositions of the woody, Oriental and orrisy type, in newvariations of Pine fragrances, and in various soap and detergentperfumes".

(iv) "1029: 3,3-DIMETHYL-Δ² - beta-NORBORNANE-2-ETHYLACETATE

"camphene carbinyl acetate". ##STR14## Mild and sweet-woody odor with afloral-piney undertone. The commercial products are probably notwell-defined single chemicals, and great variations in odor have beenobserved.

This ester has been developed in line with the research on Sandalwoodtype odors. The parent alcohol "Camphene carbinol" was once considereduseful as a Sandalwood type material, but it has found more use as asweetening and enriching ingredient in sophisticated Pine fragrances.The title ester finds limited use in perfume compositions of woodycharacter, Fougeres, Pine fragrances, etc. and it blends very well withthe Cyclohexanol derivatives, Ionones, iso-Bornylacetate, Nitromusks,etc.".

U.S. Pat. No. 3,928,456 discloses monocyclic compounds having thegeneric structure: ##STR15## containing one double bond in position 2'-or 3'- of the acyl side-chain and either one double bond in position 1-or 2- (as shown in the above formula, the double bond in the 2 positioncan be either in the cycle or the side chain), or two conjugated doublebonds in positions 1- and 3- of the cycle, the double bonds beingrepresented by dotted lines, and wherein n is zero or 1, R¹, R² and R³represent hydrogen or one of them a lower alkyl radical, such as methylor ethyl, and the others hydrogen, and R⁴, R⁵ , R⁶ and R⁷ representhydrogen or one of them a lower alkyl radical, such as methyl or ethyl,and the others hydrogen, as being useful in perfumery and food flavorsand also flavors, beverages, animal feeds and tobaccos. Specificallydisclosed in this patent is a compound having the structure: ##STR16##

U.S. Application for Letters Patent Ser. No. 551,030, filed on Feb. 19,1975 discloses, interalia, perfumery uses of compounds having thestructures: ##STR17## wherein one of the dashed lines is a carbon-carbonbond and each of the wavy lines is a carbon-carbon single bond, one ofthe carbon-carbon single bonds represented by the wavy line beingepimeric with respect to the other of the carbon-carbon single bondsrepresented by the wavy line.

In addition, various processes and compounds relating to the synthesisof synthetic sandalwood oil components are described in the followingU.S. Patents:

(i) Perfume Compounds And Process For Preparing Same-3,673,261 issuedJune 27, 1972: Compounds: ##STR18##2-methylene-3-exo-(trans-4'-methyl-5'-hydroxypent-3'-enyl)-bicyclo[2.2.1]heptane;trans-3-normethylbeta-santalol ##STR19##2-methylene-3-exo-(cis-4'-methyl-5'-hydroxypent-3'-enyl)-bicyclo[2.2.1]heptane; cis-3-normethyl-beta-santalol ##STR20##2-methylene-3-exo-(4'-methyl-5'-hydroxypentyl)-bicyclo[2.2.1]heptane;3-normethyldihydro-beta-santalol

(ii) Dihydro-beta-santalol and Processes for PreparingDihydro-beta-santalol From3-Endo-Methyl-3-Exo-(4'-Methyl-5'-Hydroxyphenyl)-Norcamphor-3,673,263issued June 27, 1972: ##STR21## dihydro-beta-santalol

(iii) Process for Preparing Beta-Santalol From 3-Methylnorcamphor -3,662,008 issued May 9, 1972: ##STR22##endo-3-methyl-exo-3-(cis-5'-hydroxy-4'-methylpent-3'-enyl)-2-methylenebicyclo[2.2.1]heptane##STR23##endo-3-methyl-exo-3-(trans-5'-hydroxy-4'-methylpent-3'-enyl)-2-methylenebicyclo[2.2.1]heptane

(iv) Process For Preparing Dihydro-Beta-Santalol From3-Endo-Methyl-3-Exo-(4'-Methyl-5'-Hydroxypentyl)-Norcamphor - 3,673,266,issued June 27, 1972: ##STR24## dihydro-beta-santalol

None of the compounds disclosed in either U.S. Pat. No. 3,928,456 orU.S. Application for Letters Patent Ser. No. 551,030, filed February 19,1975 have properties even closely similar to the properties of thecompounds of the instant application.

Chem. Abstracts, Vol. 84, 73728n (abstract of Karaev, et al, Zh. Org.Khim. 1975, 11(12), 2622) discloses preparation of the compound:##STR25## followed by isomerization with HgO/H₂ SO₄.

Klein and Rojahn, Chem. Abstracts, Vol. 84, 90327y (1976) discloses theuse of compounds having the structure: ##STR26## (wherein the dashedline is a single or double bond) as an intermediate in the preparationof beta-santalol; but no organoleptic properties of these norbornanederivatives are disclosed. U.S. Pat. No. 3,748,344, issued on July 24,1973, discloses that chemical compounds characterized by the structuralformula: ##STR27## wherein the dashed line represents the presence of asingle or a double bond wherein R₁ ', R₂ ', R₃ ', and R₄ ' eachrepresent hydrogen or lower methyl and R₅ ' represents hydrogen or loweralkyl and R₆ ' represents a polymethylene radical of from 2 to 4 carbonatoms which is unsubstituted or substituted with lower alkyl, which "asa whole exhibits a characteristic, pleasant, strong and long lastingaroma which is highly useful in the preparation of fragrancecompositions and perfume products". Various notes are described such agreen, cuminic, walnut, raw potato, earthy, camphoraceous, civet, walnutbark, neroli, anise, vegetable, menthone, animal, minty, eucalyptol,cucumber, pine and fecal. The specific ketals of our invention are notdisclosed in 3,748,344.

In addition, U.S. Pat. No. 3,748,344 discloses as chemical intermediatesfor preparing the above ketal, a compound having the generic structure:##STR28## wherein R₁ ', R₂ ', R₃ ', R₄ ', and R₅ ' have the same meaningas defined above.

However, the specific genuses and compounds of our invention are not setforth in U.S. Pat. No. 3,748,344 and all uses of them as chemicalintermediates for this genus of ketones is set forth in 3,748,344 atcolumn 3, lines 61--70.

No prediction of the organoleptic properties of the compounds of theinstant invention can be made by a study of the disclosure of 3,748,344.

Chemical Abstracts, Vol. 71, 49664z (abstract of SadykhZade, et al(U.S.S.R.). Dokl. Akad. Nauk Azerb. SSR 1968, 24(11), 38--41) disclosesthe synthesis of exo and endo forms of the compounds having thestructures: ##STR29##

Chemical Abstracts, Vol. 81, 135512m (abstract of Akhmedov, I.M., et al(Inst. Georg. Fiz. Khim., Baku, U.S.S.R.). Dokl. Akad. Nauk Az. SSR1974. 30(4), 18--21) discloses the synthesis of the compound having thestructure: ##STR30##

None of the Chemical Abstracts references discloses compounds which havea close structural relationship to the compound of the instantinvention. In any event, the organoleptic properties of the compounds ofthe Chemical Abstract references are different in kind from those of thecompounds of the instant invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates the NMR spectrum of the compound having thestructure: ##STR31## as synthesized in Example II.

FIG. 2 illustrates the Infrared spectrum of the compound having thestructure: ##STR32## as synthesized in Example II.

FIG. 3 illustrates the NMR spectrum of the cis isomer, having thestructure: ##STR33## produced according to Example III.

FIG. 4 illustrates the Infrared spectrum of the cis isomer, having thestructure: ##STR34## as synthesized in Example III.

FIG. 5 illustrates the NMR spectrum of the compound having thestructure: ##STR35## as synthesized in Example III.

FIG. 6 illustrates the Infrared spectrum of the compound having thestructure: ##STR36## as synthesized in Example III.

FIG. 7 illustrates the NMR spectrum of the compound having thestructure: ##STR37## as synthesized in Example XI.

FIG. 8 illustrates the Infrared spectrum of the compound having thestructure: ##STR38## as synthesized in Example XI.

FIG. 9 illustrates the NMR spectrum for fraction 7 of Example XIIcontaining primarily a compound having the structure: ##STR39##

FIG. 10 illustrates the Infrared spectrum for fraction 7 of Example XIIcontaining primarily a compound having the structure: ##STR40##

FIG. 11 illustrates the NMR spectrum for fraction 5 of Example XVIIwhich is a compound having the structure: ##STR41##

FIG. 12 illustrates the Infrared spectrum for fraction 5 of Example XVIIwhich is the compound having the structure: ##STR42## FIG. 13illustrates the NMR spectrum for fraction 5 of Example XIX which is thecompound having the structure: ##STR43##

FIG. 14 illustrates the Infrared spectrum for fraction 5 of Example XIXwhich is a compound having the structure: ##STR44##

FIG. 15 illustrates the GLC profile of the mixture produced according toExample XX.

FIG. 16 is an illustration of the NMR spectrum of the mixture of threecompounds in fraction 12 of Example XX, the three compounds having thestructures: ##STR45##

FIG. 17 illustrates the Infrared spectrum of fraction 12 of Example XXwhich is a mixture of the three compounds having the structures:##STR46##

FIG. 18 illustrates the NMR spectrum of peak 1 from fraction 18 ofExample XX, which is a mixture of the two ketones having the structures:##STR47##

FIG. 19 illustrates the Infrared spectrum of peak 1, fraction 18 ofExample XX, which is a mixture of the two ketones having the structures:##STR48##

FIG. 20 illustrates the NMR analysis of the keto ether producedaccording to Example XX, having the structure: ##STR49##

FIG. 21 illustrates the Infrared spectrum for the keto ether having thestructure: ##STR50## produced according to Example XX.

FIG. 22 illustrates the GLC profile for the mixture of ketones and ketoethers produced according to Example XXI, having the structures:##STR51##

FIG. 23 is an illustration of the NMR spectrum for the mixture ofketones and keto ethers produced according to Example XXI, having thestructures: ##STR52##

FIG. 24 is the Infrared spectrum for the mixture of ketones and ketoethers produced according to Example XXI, having the structures:##STR53##

FIG. 24 is the Infrared spectrum for the mixture of ketones and ketoethers produced according to Example XXI.

FIG. 25 illustrates the NMR spectrum of the compound having thestructure: ##STR54## produced according to Part A of Example XXII(fraction 4).

FIG. 26 illustrates the Infrared spectrum of the compound having thestructure: ##STR55## produced according to Part A of Example XXII(fraction 4).

FIG. 27 illustrates the NMR spectrum for the compound having thestructure: ##STR56## produced according to Part B of Example XXII(fraction 2).

FIG. 28 illustrates the Infrared spectrum for the compound having thestructure: ##STR57## produced according to Part B of Example XXII(fraction 2).

FIG. 29 illustrates the NMR spectrum for fraction 4 of Example XXIII,which is a compound having the structure: ##STR58##

FIG. 30 is the Infrared spectrum for fraction 4 of Example XXIII, whichis a compound having the structure: ##STR59##

FIG. 31 is the GLC profile for the mixture produced according to thereaction of Example XXIV, which mixture contains compounds having thestructures: ##STR60##

FIG. 32 illustrates the NMR spectrum for the compound having thestructure: ##STR61## produced according to Example XXIV.

FIG. 33 illustrates the NMR spectrum for the compound having thestructure: ##STR62## produced according to Example XXIV.

FIG. 34 illustrates the NMR spectrum for the compound having thestructure: ##STR63## produced according to Example XXIV.

FIG. 35 is the Infrared spectrum for the compound having the structure:##STR64## produced according to Example XXIV.

FIG. 36 illustratesthe NMR spectrum for the compound produced in Part A.of Example XXV, having the structure: ##STR65##

FIG. 37 illustrates the Infrared spectrum for the compound produced inPart A of Example XXV having the structure ##STR66##

FIG. 38 is the NMR spectrum for the compound produced in Part B ofExample XXV having the structure: ##STR67##

FIG. 39 is the Infrared spectrum for the compound produced in Part B ofExample XXV having the structure: ##STR68##

FIG. 40 is the NMR spectrum for the compound having the structure:##STR69## produced according to Example XXVI.

FIG. 41 is the Infrared spectrum for the compound having the structure:##STR70## produced according to Example XXVI.

FIG. 42 illustrates the NMR spectrum for the compound having thestructure: ##STR71## produced according to the process of Example XXVII.

FIG. 43 illustrates the Infrared spectrum for the compound having thestructure: ##STR72## produced according to the process of Example XXVII.

FIG. 44 illustrates the NMR spectrum for the compound having thestructure: ##STR73## produced according to the process of ExampleXXVIII.

FIG. 45 illustrates the Infrared spectrum for the compound having thestructure: ##STR74## produced according to the process of ExampleXXVIII.

FIG. 46 illustrates the NMR spectrum for the compound having thestructure: ##STR75## produced according to the process of Example XXIX.

FIG. 47 is the Infrared spectrum for the compound having the structure:##STR76## produced according to the process of Example XXIX.

FIG. 48 is the NMR spectrum for the compound having the structure:##STR77## produced according to the process of Example XXX.

FIG. 49 is the Infrared spectrum for the compound having the structure:##STR78## produced according to the process of Example XXX.

FIG. 50 is the GLC profile for the mixture (i) of the reaction productof Example XXXI, b.p. 100-111°C/0.9 mm Hg.

FIG. 51 is the NMR spectrum for the compound having the structure:##STR79## produced according to the process of Example XXXI.

FIG. 52 is the Infrared spectrum for the compound having the structure:##STR80## produced according to the process of Example XXXI.

FIG. 53 is the NMR spectrum for the compound having the structure:##STR81## produced according to the process of Example XXXI.

FIG. 54 is the Infrared spectrum for the compound having the structure:##STR82## produced according to the process of Example XXXI.

FIG. 55 is the NMR spectrum for the compound having the structure:##STR83## produced according to the process of Example XXXI.

FIG. 56 is the Infrared spectrum for the compound having the structure:##STR84## produced according to the process of Example XXXI.

FIG. 57, FIG. 58, FIG. 59 and FIG. 60 represent GC-MS profiles forcompounds produced according to the process of Example LXI.

THE INVENTION

It has now been discovered that novel solid and liquid foodstuff,chewing gum, medicinal product and toothpaste compositions and flavoringcompositions therefor having fruity, piney/green, winey, fruity-estery,cedarwood, floral, woody, balsam tree resin-like, sweet, fruity berry,incense, minty, balsam, blueberry, piney, green fruity and/or pineneedle/green aromas with piney, eugenol/clove, spicey, fruity, winey,sweet, banana-like, estery, balsam tree resin-like, woody, incense, warmtea-like, floral, cedarwood, rosey, berry, tea, astringent, bitter,camphoraceous green/earthy, green, minty, earthy, red beet-like, balsamnatural-like, balsam resin-like, rum-like and/or blueberry tastes, aswell as novel tobacco and tobacco flavoring compositions having sweet,woody, fruity, cooling aroma prior to smoking and sweet, naturaltobacco-like smoke flavor characteristics in the mainstream on smoking;as well as novel perfume compositions, colognes and perfumed articleshaving intense and pleasant, twiggy, melony, sweet, woody, fruity,spicey (nutmeg, pepper), herbaceous, fir-balsam, thujone-like, cedarleaf, camphoraceous, musty, minty, fresh cut pine/spruce, artemesia,natural-like, cresylic, borneol aromas with strong armoise-likeundertones, may be provided by the utilization of one or moresubstituted norbornane derivatives having the generic structure:##STR85## wherein each of the dashed lines represents a carbon-carbonsingle bond or a carbon-carbon double bond with the proviso that atleast one of the dashed lines is a carbon-carbon single bond; wherein nis 0 or 1 with the proviso that n is 1 when both dashed lines are singlebonds and n is 0 when one of the dashed lines is a double bond; whereinR₁ and R₂ are each the same or different hydrogen or lower alkyl;wherein Y is: ##STR86## wherein Z is one of the moieties: ##STR87##wherein R₃ and R₄ are each alkyl; wherein R₇, R₈ and R₁₀ are each thesame or different hydrogen or lower alkyl; wherein R₉ and R₉ ' takenseparately are the same or different lower alkyl, or taken together islower alkylene; wherein the dotted line represents a carbon-carbonsingle bond or a carbon-carbon double bond; and wherein each of the wavylines represents, in the alternative, exo or endo isomers, infoodstuffs, chewing gums, toothpastes, medicinal products, perfumecompositions, perfumed articles, colognes and tobaccos as well astobacco substitutes.

Unless otherwise specified, representations herein of carbon-carbondouble bonds are intended to indicate a "cis" isomer, a "trans" isomer,or a mixture of "cis" and "trans" isomers with respect to thatcarbon-carbon double bond.

The novel substituted norbornane derivatives of our invention useful asindicated supra, may be produced, preferably, by one of severalprocesses:

(1) A process comprising the step of reacting one or a mixture ofcompounds having the structures: ##STR88## wherein the dotted linerepresents a carbon-carbon single bond or a carbon-carbon double bondwith an aldehyde having the structure: ##STR89## wherein R₁ and R₁₀ arethe same or different alkyl or hydrogen as defined above, therebyforming a mixture of compounds having the two structures: ##STR90##utilizing the resulting compounds for their organoleptic properties orfurther reacting the resulting compounds, either with a Grignardreagent, R₈ MgX, or an organolithium reagent, R₈ Li, (wherein R₈ islower alkyl, e.g., methyl, ethyl, 1-propyl-2-propyl, 1-butyl, 2-butyl,2-methyl-1-butyl or 2-methyl-2-butyl) followed by hydrolysis to form thetertiary alcohol having one of the structures: ##STR91## or by reductionof the carbonyl group and/or one (or more) of the carbon-carbon doublebond(s) to form the secondary alcohol or ketone having one of thestructures: ##STR92## or by re-arranging the carbon-carbon double bondin the side chain thereby forming compounds of the structure: ##STR93##wherein R₁ and R₁₀ are the same or different hydrogen or lower alkyl,wherein the dotted line represents a carbon-carbon single bond or acarbon-carbon double bond, and wherein each of the dashed linesrepresent a carbon-carbon single bond or a carbon-carbon double bondwith the proviso that at least one of the dashed lines is acarbon-carbon single bond.

(2) Oxidizing camphene to form camphene oxide having the structure:##STR94## and then rearranging said camphene oxide to the aldehye(3,3-dimethylnorbornane-2-carboxaldehyde) having the structure:##STR95## and then reacting the aldehyde with a Grignard reagent havingthe structure: ##STR96## or an organolithium reagent having thestructure: ##STR97## wherein X is one of the halogen atoms, chlorine,bromine or iodine, thereby forming an organo-metallic compound havingthe structure: ##STR98## and then hydrolyzing the said organometalliccompound to form the corresponding alcohol having the structure:##STR99## and then using said alcohol for its organoleptic properties oroxidizing or reducing said alcohol to form either the unsaturatedketone, or the saturated alcohol, as is set forth in the first of theseprocesses (process (1)), which ketone and alcohols have the structures,respectively, ##STR100## and then using the resulting products for theirorganoleptic properties or, in the case of compounds having unsaturationin the side chain, rearranging the double bond to form a compound havingthe structure: ##STR101##

(3) Reacting an aldehyde having the structure: ##STR102## with aGrignard reagent having the structure: ##STR103## or an organolithiumreagent having the structure: ##STR104## wherein n is 0 or 1 therebyforming an organo-metallic compound having the structure: ##STR105##then hydrolyzing the resulting organometallic compound thereby formingthe saturated alcohol having the structure: ##STR106## This alcohol canthen be used as such for its organoleptic properties or it can beoxidized to form the ketone having the structure: ##STR107## or it canbe esterified with an esterification agent to form an ester having thestructure: ##STR108## wherein R₁, R₂ and R₃ are the same or differenthydrogen or alkyl and n is 0 or 1.

(4) Adding a compound, 2-acetyl-3,3-dimethyl-5-norbornene having thestructure: ##STR109## to acetaldehyde according to the reactionsequence: ##STR110## (wherein X is halogen, e.g., chloro, bromo or iodo)whereby a compound having the structure: ##STR111## is formed.

(5) Adding 2-acetyl-3,3-dimethylnorbornane having the structure##STR112## to an allylic halide having the structure: ##STR113## whereineither or both of R₁, R₂ and R₁₀ is hydrogen or lower alkyl and X is oneof the halogen atoms, chlorine, bromine or iodine, in the presence of abase such as an alkali metal hydroxide and a "phase transfer agent", orin the presence of a base such as an alkali metal hydride in thepresence of a "phase transfer agent" in order to form the compoundshaving the structures: ##STR114## wherein any of R₁, R₂, R₁₀, R₁ ', R₂ 'and R₁₀ ' are the same or different hydrogen or lower alkyl; using theresulting mixture "as is" for its organoleptic properties or separatingthe resulting mixture into its component compounds and using theresulting compounds for their organoleptic properties or furtherreacting the resulting mixture or each of the resulting compounds as byrearrangement of a carbon-carbon double bond and/or by reduction of theketo group to form a hydroxyl group or reduction of one or morecarbon-carbon double bonds using hydrogen;

(6) Reacting 2-acetyl-3,3-dimethylnorbornane or2-acetyl-3,3-dimethyl-5-norbornene with a dialkyl carbonate to form aketocarboxylic acid ester, forming the enolate of the ketocarboxylicacid ester using a base, and then reacting the resulting enolate with anallyl halide to form a substituted ketocarboxylic acid ester andsaponifying the resulting substituted ketocarboxylic acid ester to forma salt of a ketocarboxylic acid and then acidifying the salt of theketocarboxylic acid and decarboxylating the ketocarboxylic acidaccording to the following reaction sequence: ##STR115## wherein R₆ islower alkyl and R₁ and R₂ are the same or different hydrogen or loweralkyl, M₁ and M₂ are the same or different alkali metal; using theresulting ketone "as is" for its organoleptic properties or furtherreacting the resulting ketone as indicated in any of Processes 1-5,inclusive;

(7) Reacting 2-acetyl-3,3-dimethylnorbornane or2-acyl-3,3-dimethyl-5-norbornene having the generic structure:##STR116## wherein R₈ ' is lower alkyl, with an allylic Grignard reagenthaving the structure: ##STR117## or an allylic lithium reagent havingthe structure: ##STR118## wherein X is one of the halogen atoms,chlorine, bromine or iodine, thereby forming an organometallic compoundhaving the structure: ##STR119## and then hydrolyzing the organometalliccompound using aqueous mineral acid to form the corresponding tertiaryalcohol having the generic structure: ##STR120##

Each of the foregoing processes is described below in more detail.

Process 1: The reaction of the aldehyde having the structure: ##STR121##with 2-acetyl-3,3-dimethylnorbornane or2-acetyl-3,3-dimethyl-5-norbornene, preferably takes place in thepresence of either a base such as an alkali metal hydroxide (e.g., NaOH)or a mixed catalyst containing boron oxide and boric acid whereby analkenoyl norbornane or norbornene derivative is formed having thestructure: ##STR122## wherein one of the dashed lines is a carbon-carbondouble bond and the other is a single bond and the dotted linerepresents a carbon-carbon single bond or double bond; wherein R₁ andR₁₀ are the same or different hydrogen or lower alkyl. Thus, forexample, reaction of acetaldehyde with 2-acetyl-3,3-dimethylnorbornaneproduces 2-(trans-2-butenoyl)-3,3-dimethylnorbornane. It is preferred tocarry out this reaction at a temperature in the range of from 120° C upto 200° C for a period of from 3 up to 10 hours. It is preferred thatthe mole ratio of 2-acetyl-3,3-dimethylnorbornane (or norbornene)aldehyde be 1:1 or slightly greater than 1:1. When using an alkali metalhydroxide catalyst, it is preferred that the mole ratio of base:acetylnorbornane or norbornene be from 1:1 up to 20:1. When using the mixedcatalyst, boron oxide:boric acid, it is preferred that the mole ratio ofaldehyde:boron oxide be approximately 2:1 or greater than 2:1 and it ispreferred that the mole ratio of boron oxide:boric acid be between 5:1and 10:1 with a preferred ratio range of between 6:1 and 8:1. In view ofthe temperature range of reaction, 120°-180° C, this reaction is carriedout in an autoclave at autogeneous pressure. The resulting product canbe used "as is" for its organoleptic properties or it can further bereacted with an R₈ MgX (e.g. CH₃ MgBr) Grignard reagent or R₈ Li whereinR₈ is lower alkyl in a solvent (e.g., tetrahydrofuran or diethyl ether)followed by acid hydrolysis (e.g., dilute HCl) or it can further bereduced using hydrogen as a reducing agent and a hydrogenation catalystsuch as 5% palladium-on-carbon or Raney nickel. In place of the boricacid:boron oxide catalyst this reaction can be carried out using onlyboron oxide, and in that case, it is preferred to use a temperature ofbetween 170°-185° C at a pressure in the autoclave of between 40-100psig.

Process 2: The camphene epoxide is prepared from reaction of camphenewith a peralkanoic acid oxidizing agent, for example, peracetic acid orperpropionic acid. It is also preferred that the reaction take placefrom 0 up to 80° C (preferably, 40-60° C) in the presence of a solventinert to the reactants or the reaction product. Such an inert solvent ismethylene chloride. Other useful inert solvents are benzene, toluene,xylene and cyclohexane. The mole ratio of camphene:peracetic acid ispreferably slightly less than 1:1 since it is desired that all thecamphene be reacted. At the end of the reaction any excess peraceticacid is neutralized and the camphene oxide may be isolated or thereaction mass may be used "as is" for the subsequent reaction. From aneconomic standpoint, it is preferred that the reaction mass be used "asis" rather than purify the camphene oxide.

The resulting product is then rearranged to the aldehyde by heating withMgCl₂ or MgBr₂, and the resulting aldehyde is then admixed with apreprepared Grignard reagent having the formula: ##STR123## ororganolithium reagent having the structure: ##STR124## wherein X is oneof the halogen atoms chlorine, iodine or bromine and R₁ and R₂ are thesame or different hydrogen or lower alkyl. It is preferred that theGrignard reagent and the aldehyde each be respectively dissolved inappropriate solvents prior to admixing the aldehyde with the Grignardreagent. Suitable solvents for the reaction are tetrahydrofuran, diethylether, and mixtures of tetrahydrofuran or diethyl ether with benzene,toluene, xylene, or cyclohexane. It is preferred that reaction of theGrignard reagent or organolithium compound with the aldehyde take placeat a temperature in the range of from 50° C up to 100° at atmosphericpressure, preferably in the range of 65-70° C. The resultingorganometallic compound is then hydrolyzed with aqueous acid, preferablyan aqueous protonic acid such as hydrochloric acid or phosphoric acid,whereby the pH of the resulting solution is approximately 1. Theresulting alcohol, the hydrolyzed product, is then extracted from thereaction mass with a suitable inert extraction solvent such as benzene,toluene or xylene and is then isolated by means of evaporation andfractional distillation. The resulting alcohol may then be used "as is"for its organoleptic properties in perfumery, as a flavorant forfoodstuffs, in chewing gum, medicinal products or tobaccos or as aflavor for tobacco; or it may further be reacted as by oxidation orreduction.

The oxidation of the alcohol is carried out using a suitable oxidationagent such as "Jones Reagent", sodium dichromate-sulfuric acid mixture,pyridinium chlorochromate, or a chromium trioxide-acetic acid-watermixture to form the corresponding ketone. The oxidation reaction may becarried out at temperatures between -10° C and +50° C. When using aJones Reagent, it is preferred to use a temperature of about -5° C. Itis noteworthy that oxidation systems such as dimethyl sulfoxide-aceticanhydride or copper chromite have not given successful oxidations. Theresulting ketone may be hydrogenated using, for example, a palladiumcatalyst or a palladium-on-carbon catalyst, whereby a saturated ketoneis formed for example, according to the reaction: ##STR125## or theketone can be used "as is" for its organoleptic properties. Thehydrogenation is preferably carried out at temperatures in the range offrom about 20° C up to 100° C. Process 3: In the reaction of3,3-dimethylnorbornane-2-carboxaldehyde with the Grignard reagent havingthe structure: ##STR126## or the hydrocarbyl lithium compound having thestructure: ##STR127## wherein n is 0 or 1, either or both of R₁ and R₂is hydrogen or lower alkyl and X is one of the halogen atoms, chlorine,bromine or iodine, the reaction conditions are essentially the same asthose of the corresponding reaction in Process 2 and the recovery stepsare essentially the same. The resulting alcohol having the structure:##STR128## can be used as such for its organoleptic properties or it canbe oxidized to form a ketone under the conditions set forth in Process 2or it can be esterified with an esterification agent to form an esterhaving the structure: ##STR129## wherein R₃ is hydrogen or lower alkyl.Esterification agents are alkanoic acid anhydrides such as aceticanhydride, propionic anhydride, butyric anhydride; mixed anhydrides suchas acetic-propionic anhydride; acyl halides such as acetyl chloride,propionyl chloride, acetyl bromide, propionyl bromide, n-butanoylchloride, i-butanoyl chloride, n-pentanoyl chloride, n-octanoylchloride, and n-lauroyl chloride.

Process 4: The reaction sequence: ##STR130## involves a reaction ofmethyl aniline with methyl magnesium halide (chloride, bromide oriodide) preferably each in an appropriate solvent such asbenzene/tetrahydrofuran, tetrahydrofuran or diethyl ether. It is alsopreferred that the mole ratio of methyl aniline:methyl magnesium halidebe 1:1. It is further preferred that the reaction temperature producingthe compound having the structure: ##STR131## is from -5° C up to about40° C with the most preferred temperature being 20-30° C. The reactionof the above compound with acetaldehyde preferably takes place in thepresence of an appropriate solvent such as benzene-tetrahydrofuran,tetrahydrofuran, or diethyl ether at a temperature in the range of from-5° C up to 20° C, with a preferred temperature of 0° C. The hydrolysisto form the keto alcohol is carried out using a mineral acid such asdilute aqueous hydrochloric acid, sulfuric acid or phosphoric acid orother protonic acids such as paratoluenesulfonic acid. The hydrolysispreferably takes place at 0° C. The dehydration reaction using the ketoalcohol is carried out with a mild dehydrate agent such as a mixture ofacetic anhydride and sodium acetate at a temperature in the range of80-150° C over a period of time of from about 1 up to 5 hours. Thedehydration can also be carried out using a strong acid in a refluxinginert solvent, e.g., using a benzene-paratoluenesulfonic acid mixture.At the end of this reaction the excess dehydration agent, e.g. aceticanhydride, is destroyed and the reaction product isolated. Using thisreaction sequence, only "trans" isomer is formed. If the startingmaterial is "endo" 2-acetyl-3,3-dimethyl-5-norbornene, then the finalproduct will also be an "endo" isomer. By the same token, if thestarting material is "exo" 2-acetyl-3,3-dimethyl-5-norbornene, then thefinal product will be an "exo" isomer. Standard isolation techniques areused, e.g. fractional distillation and, if desired, preparative GLC forisolation of the end product.

Process 5: The reaction of 2-acetyl-3,3-dimethylnorbornane with theallyl chloride derivative takes place after first forming the enolate ofthe 2-acetyl-3,3dimethyl-norbornane, thusly: ##STR132## The reagent usedto form such enolate is preferably a hydride such as sodium hydride andpotassium hydride. The enolate is then reacted with the allyl halidehaving the structure: ##STR133## Wherein R₁ and R₂ are the same ordifferent hydrogen or lower alkyl and X is one of the halogen atoms,chlorine, bromine or iodine. In addition, a similar result may beobtained when using an alkali metal hydroxide in the presence of a phasetransfer agent whereby the reactants for the process and the base,respectively, are in two immiscible phases and the phase transfer agentmay be one or more of several quaternary salts. Specific examples ofphase transfer agents useful in our invention are as follows:

Tricapryl methyl ammonium chloride;

Cetyl trimethyl ammonium bromide; and

Benzyl trimethyl ammonium hydroxide. In general, the phase transferagents most preferred have the generic formula: ##STR134## wherein atleast one of R₁₁, R₁₂, R₁₃ and R₁₄ is C₆ -C₁₄ aryl, C₆ -C₁₀ aralkyl, C₆-C₂₀ alkyl, C₆ -C₁₄ alkaryl and C₆ -C₂₀ alkenyl and the other of R₁₂,R₁₃, R₁₄ is alkyl such as methyl, ethyl, n-propyl, i-propyl, l-butyl,2-butyl, 1-methyl-2-propyl, 1-pentyl and 1-octyl and Z⁻ in an anion suchas chloride, bromine and hydroxide. Furthermore, this process is carriedout in an inexpensive solvent which is inert to the reaction system suchas toluene, benzene, o-xylene, m-xylene, p-xylene, ethyl benzene,n-hexane, cyclohexane, methylene chloride and o-dichlorobenzene. ThisProcess (5) of our invention is carried out at a temperature in therange of from about 10° C up to about 150° with a temperature range of50-120° being preferred. The reaction time is inversely proportional tothe reaction temperature, with lower reaction temperatures giving riseto greater reaction times; and, accordingly, the reaction time rangesfrom about 30 minutes up to about 10 hours.

In this reaction of our invention the mole ratio of2-acetyl-3,3-dimethylnorbornane:allyl halide reactant is in the range offrom 0.5:1.5 up to 1.5:0.5 with a preferred ratio of norbornane:allylhalide being from 1:1 up to 1:1.2.

The quantity of "phase transfer agent" in the reaction mass, based uponthe amount of 2-acetyl-3,3-dimethylnorbornane in the reaction mass, mayvary from 0.5 grams of "phase transfer agent" per mole of norbornanederivative to 25 grams of "phase transfer agent" per mole of norbornanederivative with a preferred concentration of "phase transfer agent"being in the range of from 2.5 up to about 7.5 grams of "phase transferagent" per mole of norbornane derivative.

Process (5) of our invention is preferably carried out at atmosphericpressure since that is the most convenient condition. However, lower orhigher pressures can be used without detrimentally affecting theultimate yield of desired reaction product.

Process 6: The initial compound formed is that created by reaction ofthe dialkyl carbonate with 2-acetyl-3,3-dimethylnorbornane in thepresence of an alkali metal hydride, as illustrated by the followingreaction: ##STR135## wherein R₆ is alkyl having from 1 up to 8 carbonatoms, but most conveniently ethyl. The reaction is preferably carriedout under reflux conditions using a solvent inert to the reactants suchas benzene, toluene or xylene. The mole ratio of norbornane derivative:dialkyl carbonate is preferably 1:2; but can vary from 1:1 up to 1:5.The ratio of base:dialkyl carbonate is preferably 1:1.

The reaction of the resulting beta-ketocarboxylic acid ester with theallyl halide having the structure: ##STR136## (wherein X is a halogen,chlorine, bromine or iodine and R₁, R₂ and R₁₀ are the same or differenthydrogen or lower alkyl), is carried out in the presence ofapproximately one equivalent of base such as an alkali metal hydride oralkali metal alkoxide or hydroxide in the presence of a suitablesolvent. A "phase transfer agent" may be used. The ketocarboxylic acidester derivative has the structure: ##STR137## This ketocarboxylate, (anovel genus of compounds), is then saponified using standard techniquessuch as with an aqueous base such as 5-25% aqueous sodium hydroxide orpotassium hydroxide, and the resulting alkali metal salt having thestructure: ##STR138## (wherein M is alkali metal), is then neutralizedand simultaneously decarboxylated using aqueous mineral acid such assulfuric acid or aqueous hydrochloric acid. The resulting reactionproduct having the structure: ##STR139## (a mixture of cis and transisomers; wherein R₁ and R₂ is alkyl) may then be used for itsorganoleptic properties "as is" or it may be hydrogenated with hydrogenusing a catalyst such as palladium, palladium-on-carbon or Raney nickel,whereupon the carbon-carbon double bond in the side chain is reduced toa carbon-carbon single bond thereby forming a compound having thestructure. ##STR140## Both the unsaturated ketone and the saturatedketone may be reacted, if desired, with an alcohol or glycol in thepresence of sulfuric acid or hydrochloric acid thereby forming a ketalaccording to the reaction: ##STR141## wherein R₉ and R₉ ' each representlower alkyl taken separately or, when taken together, represents loweralkylene, e.g. ethylene; and wherein the dashed line represents acarbon-carbon single bond or a carbon-carbon double bond. Alternatively,either ketone may be converted into its corresponding oxime by usinghydroxylamine or hydroxylamine acid salts such as hydroxylamine orhydrochloride whereby an oxime having the structure: ##STR142## isformed. Such ketals and oximes also have useful organoleptic properties.

Process 7: In the reaction of the 2-acyl-3,3-dimethylnorbornane or the2-acyl-3,3-dimethyl-5-norbornene with the Grignard reagent having thestructure: ##STR143## wherein R₁, R₂ and R₁₀ are separately hydrogen orlower alkyl and X is one of the halogen atoms, chlorine, bromine oriodine, the reaction conditions are essentially the same as those of thecorresponding reaction in Process (2) and the recovery steps areessentially the same. R₈ ' of the generic structure: ##STR144## isdefined wherein R₈ ' is lower alkyl such as methyl, ethyl, n-propyl,i-propyl, n-butyl, i-butyl, n-pentyl and n-octyl. The resulting alcoholhaving the structure: ##STR145## can be esterified in accordance withthe corresponding reaction detailed in the Process (3) description,supra.

Specific examples of the compounds produced according to the foregoingprocesses are set forth in Table I below:

                                      TABLE I                                     __________________________________________________________________________    STRUCTURE         NAME       PERFUMERY    FLAVOR     TOBACCO                  OF COMPOUND       OF COMPOUND                                                                              EVALUATION   EVALUATION EVALUATION               __________________________________________________________________________     ##STR146##       2(2-butenoyl)- 3,3-dimethyl- norbornane                                                  Sweet, woody, fruity, spicey (nutmeg,                                         pepper), herbaceous aroma with pine needle                                    nuances.     Fruity, pine needle/ green,                                                   winey aroma with piney,                                                       eugenol/ clove, spicey, fruity,                                               winey flavor.                       cis and trans                                                                  ##STR147##       2-(3'-butenoyl)-3,3- dimethylnorbornane                                                  Fruity, herbaceous, piney aroma with armoise                                  character and fir-balsam character- istics.                                                Fruity-estery, cedarwood,                                                     floral, woody, balsam tree                                                    resin-like aroma with sweet,                                                  fruity, banana-like, estery,                                                  balsam tree resin- like, piney                                                flavor character.                    ##STR148##       alpha-allyl-3,3-  dimethyl-2-norbor- nanemethanol                                        Sweet, woody, thujone- like aroma with                                        armoise, cedar leaf, piney and camphoraceous                                  nuances.     A sweet, fruity berry aroma                                                   with woody, incense, warm                                                     tea-like, floral nuances and an                                               incense and cedarwood flavor                                                  with rosey, berry and tea                                                     nuances.   A woody, sweet,                                                               fruity, cooling                                                               aroma and taste                                                               before and on                                                                 smoking.                  ##STR149##       alpha-methallyl- 3,3-dimethyl-2- norbornanemethanol                                      Fruity, musty, sweet, woody, minty aroma                                      with fresh cut pine/spruce nuances.                                                        Incense and woody aroma and an                                                incense and woody flavor with                                                 astrin- gent and bitter notes.       ##STR150##       alpha-ethyl-3,3- dimethyl-2-norbor- nanemethanol                                         Musty, sweet fruity, woody aroma with                                         artemesia character- istics.                                                               A sweet, woody, minty aroma                                                   with camphoraceous green/                                                     earthy nuances and a woody,                                                   green and minty flavor with                                                   spicey, earthy, red beet-like                                                 and cam- phoraceous nuances as                                                well as a cool- ing effect.          ##STR151##       endo-2(2'-butenoyl)- 3,3-dimethyl-5- norbornane                                          Woody, piney, natural- like aroma with                                        fruity, spicey, cresylic, bor- neol nuances,                                  as well as a definitive berry top                                                          Balsam, blueberry, piney, green                                               fruity, woody aroma with balsam                                               natural-like, balsam                                                          resin-like, piney, woody and                                                  blueberry flavor characteristics                                              .                                   cis and trans                                                                  ##STR152##       Mixture of 2- acetyl-2-allyl-3,3- dimethylnorbor- nane                        and 3,3-di- methyl-2-(4'-penten- oyl)-norbornane                                         Camphoraceous, woody, fruity (orange) aroma                                   with green, piney undertones.                     ##STR153##                                                                    ##STR154##       2-(cis-2'-buten-1'- oyl)-3,3-dimethyl)- norbornane                                       Intense, piney, fruity, with floral, berry                                    and cologne nuances.                              ##STR155##       3,3-dimethyl-2-(4'- pentanoyl)-norbor- nane                                              A sweet, fruity, fir- balsam, floral aroma                                    with woody and pine- apple                                                                 Sweet, fruity, pine- apple,                                                   green, woody, apple juice-like,                                               iney aroma char- acter with                                                   berry, piney, oriental- like                                                  and woody flavor character.          ##STR156##       3,3-dimethyl-2- pentanoylnorbor- nane                                                    Sweet, fruity, fir- balsam aroma with floral                                  (ylang, jasmin) and berry notes.                                                           A sweet, fruity/ berry,                                                       raspberry, woody and plum aroma                                               with sweet, fruity/berry,                                                     raspberry, val- orian oil-like,                                               oody and plum flavor character-                                               stics.                               ##STR157##       3,3-dimethyl-alpha- propyl-2-norbornane- methanol                                        Camphoraceous, woody, green aroma with minty                                  uances.      A sweet, delicate piney,                                                      fruity, berry- like, valerian                                                 oil- like, woody aroma with                                                   sweet, delicate piney,                                                        evergreen- like, valerian oil-                                                like, fruity, berry and                                                       astringent flavor characteristic                                              s.                                   ##STR158##       2-butyryl-3,3- dimethylporborane                                                         A sweet, piney needle- like, fruity,                                          camphor- aceous aroma.                                                                     A sweet, delicate, piney,                                                     fruity, fir balsam needle oil-                                                like, blueberry, woody and                                                    straw- berry-like aroma with                                                  sweet, delicate piney,                                                        blueberry, juniper-like, straw-                                               erry and astringent nuances.         ##STR159##       Mixture of 3,3- dimethyl-2(4'- methyl-4'-pentenoyl)-                          norbornane and 3,3- dimethyl-2-acetyl- 2(2'-methyl-2'-                        propenyl)-norbornane                                                                     A fruity, woody, low- keyed but long lasting                                  roma.        A camphoraceous, woody and                                                    minty aroma with a strong                                                     cooling nuance and a strong,                                                  woody and minty                                                                          A woody aroma, prior                                                          to and on smoking                                                             with sweet, spicey,                                                           floral naunces.           ##STR160##                                                                    ##STR161##       2-acetyl-2-meth- allyl-3,3-dimethyl- norbornane                                          A low-keyed, sweet, camphoraceous, woody                                      (cedarwood) aroma with green, herbaceous and                                  piney nuances.                                    ##STR162##       3,3-dimethyl-2-(2- methallyl-4'-  methyl-4'-penten-                           oyl)-norbornane                                                                          A low-keyed, sweet, green, woody, herb-                                       aceous aroma with a waxy nuance.                 Mixture of:                                                                    ##STR163##       Mixture of 3,3- dimethyl-2-(4'- methyl-2'-penten-                             oyl)-norbornane; 3,3-dimethyl-2-(4'-                                          methyl-3'-pentenoyl)- norbornane; and                                         3,3- dimethyl-2-(4'-methyl- 3-methoxypentenoyl)-                              norbornane A long lasting, excellent, fruity and berry                                   aroma.       A fruity, rasp- berry and sweet                                               roma with a green nuance and a                                                fruity, rasp- berry, green                                                    flavor with a bitter                                                                     A sweet, fruity-                                                              raspberry-like aroma                                                          prior to smoking and                                                          a sweet, fruity,                                                              raspberry aroma with                                                          green nuances on                                                              smoking, when used                                                            in both the tobacco                                                           and in the filter.         +                                                                            ##STR164##                                                                     +                                                                            ##STR165##                                                                   Mixture of:                                                                    ##STR166##       Mixture of 3,3-dim- ethyl-2-(4-'-methyl- 2'-pentenoyl)-5                      - norbornane; 3,3-dim- ethyl-2-(4'-methyl- 3-pentenoyl)-                      5- norbornene; and 3,3- dimethyl-2-(4' -methyl-                               3-methoxypentenoyl)- 5-norbornene                                                        A fruity, berry-like aroma.                                                                A sweet, rod berry jam-like,                                                  fruity aroma with citrus,                                                     ionone-like, berry-like, pine                                                 needle-like and pungent nuances                                               nd a fruity, red berry-like,                                                  berry jam-like flavor with                                                    green, fresh raspberry and                                                    piney nuances.                                                                           A sweet, floral and                                                           green aroma prior to                                                          smoking, and a                                                                sweet, fruity,                                                                floral aroma on                                                               smoking in the                                                                mainstream and in                                                             the side- stream.          +                                                                            ##STR167##                                                                     +                                                                            ##STR168##                                                                    ##STR169##       alpha-ethyl-3,3- dimethyl-2-nor- bornanemethanol                                         A minty, sweet fruity, woody aroma with some                                  rtemesia character and, in addition,                                          herbaceous and pine needle                                                                 A sweet, woody,  minty aroma                                                  with green and earthy nuances                                                 and a woody, green minty flavor                                               with spicey, earthy, cooling                                                  and red beet nuances.                                                                    A sweet, woody,                                                               piney aroma and a                                                             strong, cooling                                                               effect when used in                                                           the filter, both                                                              prior to, and, on                                                             smoking. Also                                                                 reduces harshness                                                             and gives rise to a                                                           "fresh" effect.           ##STR170##       alpha-allyl-alpha- 3,3-trimethyl-2- norbornanemethanol                                   Low-keyed, sweet, woody (cut pine)                                                         Sweet, earthy, piney, cedarwood                                               roma with sweet, cedarwood,                                                   fruity, blueberry-like flavor                                                 with patch- ouli and walnut                                                   nuances.                             ##STR171##       alpha-allyl-alpha- 3,3-trimethyl-5- norbornane-2-                             methanol   A sweet, minty, fruity, slight melony, woody                                  roma.        A piney, fruity, woody,                                                       patchouli- like, carrot, walnut                                               aroma with a sweet, fruity,                                                   woody, camphora- ceous, carrot,                                               ried apple, patchouli-like,                                                   walnut and astrin- gent             __________________________________________________________________________                                              flavor.                         

When the norbornane derivatives of our invention are used as food flavoradjuvants, the nature of the co-ingredients included with each of thesaid norbornane derivatives in formulating the product composition willalso serve to alter, modify, augment or enhance the organolepticcharacteristics of the ultimate foodstuff treated therewith.

As used herein in regard to flavors, the terms "alter", "modify" and"augment" in their various forms mean "supplying or imparting flavorcharacter or note to otherwise bland, relatively tasteless substances oraugmenting the existing flavor characteristic where a natural flavor isdeficient in some regard or supplementing the existing flavor impressionto modify its quality, character or taste".

The term "enhance" is used herein to mean the intensification of aflavor or aroma characteristic or note without the modification of thequality thereof. Thus, "enhancement" of a flavor or aroma means that theenhancement agent does not add any additional flavor note.

As used herein, the term "foodstuff" includes both solid and liquidingestible materials which usually do, but need not, have nutritionalvalue. Thus, foodstuffs include soups, convenience foods, beverages,dairy products, candies, vegetables, cereals, soft drinks, snacks andthe like.

As used herein, the term "medicinal product" includes both solids andliquids which are ingestible non-toxic materials which have medicinalvalue such as cough syrups, cough drops, aspirin and chewable medicinaltablets.

The term "chewing gum" is intended to mean a composition which comprisesa substantially water-insoluble, chewable plastic gum base such aschicle, or substitutes therefor, including jelutong, guttakay, rubber orcertain comestible natural or synthetic resins or waxes. Incorporatedwith the gum base in admixture therewith may be plasticizers orsoftening agents, e.g., glycerine; and a flavoring composition whichincorporates one or more of the norbornane derivatives of our invention,and in addition, sweetening agents which may be sugars, includingsucrose or dextrose and/or artificial sweetners such as cyclamates orsaccharin. Other optional ingredients may also be present.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use, being extensivelydescribed in the relevant literature. It is a requirement that any suchmaterial be "ingestibly" acceptable and thus non-toxic and otherwisenon-deleterious particularly from an organoleptic standpoint whereby theultimate flavor and/or aroma of the consumable material used is notcaused to have unacceptable aroma and taste nuances. Such materials mayin general be characterized as flavoring adjuvants or vehiclescomprising broadly stabilizers, thickeners, surface active agents,conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride;antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxyanisole (mixture of 2- and3-tertiary-butyl-4-hydroxyanisole), butylated hydroxytoluene(2,6-di-tertiary-butyl-4-methylphenol), propyl gallate and the like andsequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agar agar,carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatin, proteinaceous materials; lipids;carbohydrates; starches, pectines, and emulsifiers, e.g., mono- anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g., sucrose corn syrup and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono- and diglycerides of fatty acids, lecithin, defoaming andflavor-dispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, tumeric and curcuma and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers, anti-caking agents, e.g., aluminumcalcium sulfate and tribasic calcium phosphate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include aldehydes, esters,natural oils, alcohols, sulfides, ketones, lactones, carboxylic acidsand hydrocarbons such as heliotropin, terpinenol-4, benzaldehyde,anisaldehyde, phenyl acetaldehyde, benzyl formate, benzyl acetate,cis-3-hexenyl benzoate, methyl hexanoate, hexanal, eucalyptol, eugenol,acetaldehyde, ethyl acetate, ethyl butyrate, turpentine gum oil,limonene, gum camphor, isobornyl acetate, borneol, cinnamic aldehyde,cuminic aldehyde, furfural, methyl cinnamate, cassia oil, vanillin,maltol, parahydroxybenzyl acetone, dimethyl sulfide, alpha-ionone,acetic acid, isobutyl acetate, acetone, butyric acid, formic acid,valeric acid, amyl acetate, amyl butyrate, anethol, benzyl salicylate,diacetyl, dimethyl anthranilate, ethyl methylphenylglycidate, ethylsuccinate, ethyl valerate, geraniol, cis-3-hexen-1ol, 2-hexenyl acetate,2-hexenyl butyrate, hexyl butyrate, 4-(p-hydroxyphenyl)-2-butanone,beta-ionone, isobutyl cinnamate, jasmine, lemon essential oil, methylbutyrate, methyl caproate, methyl disulfide, methyl p-naphthyl ketone,orris butter, rose absolute, terpenyl acetate, gammaundecalactone,vanilla and alcohol.

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., foodstuff, whether simulated or natural, and should, in any event,(i) be organoleptically compatible with the norbornane derivatives ofour invention by not covering or spoiling the organoleptic properties(aroma and/or taste) thereof; (ii) be nonreactive with the norbornanederivatives of our invention and (iii) be capable of providing anenvironment in which the norbornane derivatives can be dispersed oradmixed to provide a homogenous medium. In addition, selection of one ormore flavoring adjuvants, as well as the quantities thereof will dependupon the precise organoleptic character desired in the finished product.Thus, in the case of flavoring compositions, ingredient selection willvary in accordance with the foodstuff, chewing gum, medicinal product ortoothpaste to which the flavor and/or aroma are to be imparted,modified, altered or enhanced. In contradistinction, in the preparationof solid products, e.g., simulated foodstuffs, ingredients capable ofproviding normally solid compositions should be selected such as variouscellulose derivatives.

As will be appreciated by those skilled in the art, the amount ofnorbornane derivatives employed in a particular instance can vary over arelatively wide range, depending upon the desired organoleptic effectsto be achieved. Thus, correspondingly, greater amounts would benecessary in those instances wherein the ultimate food composition to beflavored is relatively bland to the taste, whereas relatively minorquantities may suffice for purposes of enhancing the composition merelydeficient in natural flavor or aroma. The primary requirement is thatthe amount selected to be effective, i.e., sufficient to alter, modifyor enhance the organoleptic characteristics of the parent composition,whether foodstuff per se, chewing gum, per se, medicinal product per se,toothpaste per se, of flavoring composition.

The use of insufficient quantities of norbornane derivatives will, ofcourse, substantially vitiate any possibility of obtaining the desiredresults while excess quantities prove needlessly costly and, in extremecases, may disrupt the flavor-aroma balance, thus providingself-defeating. Accordingly, the terminology "effective amount" and"sufficient amount" is to be accorded a significance in the context ofthe present invention consistent with the obtention of desired flavoringeffects.

Thus, and with respect to ultimate food compositions, chewing gumcompositions, medicinal product compositions and toothpastecompositions, it is found that quantities of norbornane derivativesranging from a small but effective amount, e.g., 0.5 parts per millionup to about 500 parts per million based on total composition aresuitable. Concentrations in excess of the maximum quantity stated arenot normally recommended, since they fail to prove commensurateenhancement of organoleptic properties. In those instances, wherein thenorbornane derivatives are added to the foodstuff as an integralcomponent of a flavoring composition, it is, of course, essential thatthe total quantity of flavoring composition employed be sufficient toyield an effective norbornane derivative concentration in the foodstuffproduct.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain the norbornane derivatives inconcentrations ranging from about 0.1% up to about 15% by weight basedon the total weight of the said flavoring composition.

The composition described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitdrinks and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing the norbornane derivatives with, forexample, gum arabic, gum tragacanth, carrageenan and the like, andthereafter spray-drying the resultant mixture whereby to obtain theparticular soild product. Pre-prepared flavor mixes in powder form,e.g., a fruit-flavored powder mix are obtained by mixing the dried solidcomponents, e.g., starch, sugar and the like and norbornane derivativesin a dry blender until the requisite degree of uniformity is achieved.

It is presently preferred to combine with the norbornane derivatives ofour invention, the following adjuvants:

Heliotropin;

Terpinenol-4;

Benzaldehyde;

Anisaldehyde;

Phenyl acetaldehyde;

Benzyl formate;

Benzyl acetate;

Cis-3-hexenyl benzoate;

Methyl hexanoate;

Hexanal;

Eucalyptol;

Eugenol;

Acetaldehyde;

Ethyl acetate;

Ethyl butyrate;

Turpentine gum oil;

Limonene;

Gum camphor;

Isobornyl acetate;

Borneol;

Cinnamic aldehyde;

Cuminic aldehyde;

Furfural;

Methyl cinnamate,

Cassia oil;

Vanillin;

Maltol;

Parahydroxybenzylacetone;

Dimethyl sulfide;

Alpha-ionone;

Acetic acid;

Isobutyl acetate;

Acetone;

Butyric acid;

Formic acid;

Valeric acid;

Amyl acetate;

Amyl butyrate;

Anethol;

Benzyl salicylate;

Diacetyl;

Dimethyl anthranilate;

Ethyl methylphenylglycidate;

Ethyl succinate;

Ethyl valerate;

Geraniol;

Cis-3-hexen-1-ol;

2-Hexenyl acetate;

2-Hexenyl butyrate;

Hexyl butyrate;

4-(p-Hydroxyphenyl)-2-butanone;

Beta-ionone;

Isobutyl cinnamate;

Jasmine;

Lemon essential oil;

Methyl butyrate;

Methyl capronate;

Methyl disulfide;

Methyl p-naphthyl ketone;

Orris butter;

Rose absolute;

Terpenyl acetate;

Gamma-undecalactone,

Vanilla; and

Alcohol.

An additional aspect of our invention provides an organolepticallyimproved smoking tobacco product and additives therefor, as well asmethods of making the same which overcome problems heretoforeencountered in which specific desired sweet, woody, piney and fruityflavor characteristics of natural tobacco (prior to smoking and, onsmoking, in the mainstream and in the sidestream) as well as coolingeffects, are created or enhanced or modified for augmented and may bereadily controlled and maintained at the desired uniform levelregardless of variations in the tobacco components of the blend.

This invention further provides improved tobacco additives and methodswhereby various desirable natural aromatic tobacco flavoringcharacteristics with sweet, woody, piney, cooling and fruity notes maybe imparted to smoking tobacco products and may be readily varied andcontrolled to produce the desired uniform flavoring characteristics.

In carrying out this aspect of our invention, we add to smoking tobaccomaterials or a suitable substitute therefor (e.g., dried lettuce leaves)an aroma and flavor additive containing as an active ingredient one ormore norbornane derivatives of our invention.

In addition to the norbornane derivatives of our invention otherflavoring and aroma additives may be added to the smoking tobaccomaterial or substitute therefor either separately or in mixture with thenorbornane derivatives as follows:

I. synthetic Materials:

Beta-ethyl-cinnamaldehyde;

Eugenol;

Dipentene;

Damascenone;

Maltol;

Ethyl maltol;

Delta undecalactone;

Delta decalactone;

Benzaldehyde;

Amyl acetate;

Ethyl butyrate;

Ethyl valerate;

Ethyl acetate;

2-Hexenol-1;

2-Methyl-5-isopropyl-1,3-nonadiene-8-one;

2,6-Dimethyl-2,6-undecadiene-10-one;

2-Methyl-5-isopropylacetophenone;

2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-decahydronaphthalene;

Dodecahydro-3a,6,6,9a-tetramethylnaphtho-(2,1-b)-furan

4-Hydroxyhexanoic acid, gamma lactone; and

Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No.3,589,372 issued on June 29, 1971.

Ii. natural Oils:

Celery seed oil;

Coffe extract;

Bergamot Oil;

Cocoa extract;

Nutmeg Oil; and

Origanum Oil.

An aroma and flavoring concentrate containing one or more norbornanederivatives of our invention and, if desired, one or more of the aboveindicated additional flavoring additives may be added to the smokingtobacco material, to the filter or to the leaf or paper wrapper. Thesmoking tobacco material may be shredded, cured, cased and blendedtobacco material or reconstituted tobacco material or tobaccosubstitutes (e.g., lettuce leaves) or mixtures thereof. The proportionsof flavoring additives may be varied in accordance with taste butinsofar as enhancement or the imparting of natural and/or sweet notesand/or cooling notes and/or fruity notes and/or woody notes, we havefound that satisfactory results are obtained if the proportion by weightof the sum total of norbornane derivative(s) to smoking tobacco materialis between 50 ppm and 1,500 ppm (.015%-.15%). We have further found thatsatisfactory results are obtained if the proportion by weight of the sumtotal of norbornane derivative used to flavoring material is between1,500 and 15,000 ppm (0.15%-1.5%).

Any convenient method for incorporating the norbornane derivative(s)into the tobacco product may be employed. Thus, the norbornanederivative(s) taken alone or along with other flavoring additives may bedissolved in a suitable solvent such as ethanol, diethyl ether and/orvolative organic solvents and the resulting solution may either bespread on the cured, cased and blended tobacco material or the tobaccomaterial may be dipped into such solution. Under certain circumstances,a solution of the norbornane derivative(s) taken alone or taken furthertogether with other flavoring additives as set forth above, may beapplied by means of a suitable applicator such as a brush or roller onthe paper or leaf wrapper for the smoking product, or it may be appliedto the filter by either spraying, or dipping, or coating.

Furthermore, it will be apparent that only a portion of the tobacco orsubstitute therefor need be treated and the thus treated tobacco may beblended with other tobaccos before the ultimate tobacco product isformed. In such cases, the tobacco treated may have the norbornanederivative(s) in excess of the amounts or concentrations above indicatedso that when blended with other tobaccos, the final product will havethe percentage within the indicated range.

In accordance with one specific example of our invention, an aged, curedand shredded domestic burley tobacco is sprayed with a 20% ethyl alcoholsolution of 2-(2-butenoyl)-3,3-dimethylnorbornane having the structure:##STR172## in an amount to provide a tobacco composition containing 800ppm by weight of 2-(2-butenoyl)-3,3-dimethylnorbornane on a dry basis.Thereafter, the alcohol is removed by evaporation and the tobacco ismanufactured into cigarettes by the usual techniques. The cigarette whentreated as indicated has a desired and pleasing aroma which isdetectable in the main and sidestreams when the cigarette is smoked.This aroma is described as being sweeter, more aromatic, moretobacco-like and having sweet, fruity notes.

While our invention is particularly useful in the manufacture of smokingtobacco, such as cigarette tobacco, cigar tobacco and pipe tobacco,other tobacco products, formed from sheeted tobacco dust or fines mayalso be used. Likewise, the norbornane derivative(s) of our inventioncan be incorporated with materials such as filter tip materials (e.g.cellulose acetate filters wherein sweet, woody, piney and/or coolingeffects are desired), seam paste, packaging materials and the like whichare used along with tobacco to form a product adapted for smoking.Futhermore, the norbornane derivative(s) can be added to certain tobaccosubstitutes of natural or synthetic origin (e.g., dried lettuce leaves)and, accordingly, by the term "tobacco" as used throughout thisspecification is meant any composition intended for human consumption bysmoking or otherwise, whether composed of tobacco plant parts orsubstitute materials or both.

The norbornane derivative(s) and one or more auxiliary perfumeingredients, including, for example, hydrocarbons, alcohols, ketones,aldehydes, nitriles, esters, lactones or cyclic esters, syntheticessential oils and natural essential oils, may be admixed so that thecombined odors of the individual components produce a pleasant anddesired fragrance, particularly and preferably in woody and/or pineyfragrances. Such perfume compositions usually contain (a) the main noteor the "bouquet" or foundation stone of the composition; (b) modifierswhich round off and accompany the main note; (c) fixatives which includeodorous substances which lend a particular note to the perfumethroughout all stages of evaporation and substances which retardevaporation; and (d) topnotes which are usually low boiling freshsmelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olfactory characteristics, however theover-all sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, one or moreof the norbornane derivative(s) of our invention can be used to alter,modify or enhance the aroma characteristics of a perfume composition,for example, by utilizing or moderating the olfactory reactioncontributed by another ingredient in the composition.

The amount of norbornane derivative(s) of our invention which will beeffective in perfume compositions as well as in perfumed articles andcolognes depends on many factors, including the other ingredients, theiramounts and the effects which are desired. It has been found thatperfume compositions containing as little as 0.01% of norbornanederivative(s) or even less (e.g., 0.005%) can be used to impart a sweet,piney, woody, floral, fruity odor with berry, evergreen-like andtobacco-like nuances to soaps, cosmetics, detergents (including anionic,non-ionic and cationic detergents) or other products. The amountemployed can range up to 70% of the fragrance components and will dependon considerations of cost, nature of the end product, the effect desiredon the finished product and the particular fragrance sought.

The norbornance derivative(s) of our invention are useful (taken aloneor together with other ingredients in perfume compositions) indetergents and soaps, space odorants and deodorants, perfumes, colognes,toilet water, bath preparations, such as lacquers, brilliantines,pomades and shampoos; cosmetic preparations, such as creams, deodorants,hand lotions and sun screens; powders, such as talcs, dusting powders,face powders and the like. As little as 1% of norbornane derivative(s)will suffice to impart an intense piney note to woody perfumeformulations. Generally, no more than 3% of norbornane derivative(s)based on the ultimate end product, is required in the perfumecomposition.

In addition, the perfume composition or fragrance composition of ourinvention can contain a vehicle, or carrier for the norbornanederivative(s). The vehicle can be a liquid such as a non-toxic alcohol,a non-toxic glycol, or the like. The carrier can also be an absorbentsolid, such as a gum (e.g., gum arabic), or components for encapsulatingthe composition (such as gelatin).

It will thus be apparent that the norbornane derivative(s) of ourinvention can be utilized to alter, modify or enhance sensoryproperties, particularly organoleptic properties, such as flavor(s)and/or fragrance(s) of a wide variety of consumable materials.

Examples I-XXXI, following, serve to illustrate processes forspecifically producing the norbornane derivatives useful in ourinvention.

The following examples serve to illustrate specific embodiments of ourinvention.

It will be understood that these Examples are illustrative and theinvention is to be considered restricted thereto only as indicated inthe appended claims.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE I PREPARATION OF 3,3-DIMETHYL-2-NORBORNANECARBOXALDEHYDE

Reaction: ##STR173## Procedure:

Into a 3 liter flask fitted with a stirrer, addition funnel, refluxcondenser and thermometer are placed the following materials:

Camphene (80%): 500 g

Methylene chloride: 500 cc

Sodium carbonate: 300 g

The slurry is stirred while 600 cc of peracetic acid (40%) is added overa six hour period. The temperature rises until the mixture is at reflux(44° C in the beginning, 48° C at the end of the addition). The courseof the reaction is monitored by GLC. The mixture is allowed to stir for2 hours after the completion of the addition. The salts are then removedby filtration. The methylene chloride is stripped off and 500 cc ofbenzene is added. The mixture is azeotroped using a water separationtrap to remove traces of water. After all water is removed, the mixture(670 g) is ready for use in the next step. A GLC (samples are preparedby dissolving the salts in water, separating the organic layer andwashing it several times with water. The GLC conditions are: 10 foot ×1/8 inch SE-30 column, programmed at 80-200° at 8° C per minute)indicated 26% benzene, 9.6% tricyclene and 61.2% camphene oxide,corresponding to a yield of 408 g of camphene oxide, or 92% of theory.

50 Grams of magnesium bromide is added and the mixture is refluxed forfour hours. At the end of this time a GLC analysis (10 foot × 1/8 inchCarbowax 20M column, programmed from 80-220° C at 8° C/minute) showscomplete conversion of the camphene oxide to3,3-dimethyl-2-norbornanecarboxaldehyde.

EXAMPLE II PREPARATION OF ALPHA-ALLYL-3,3-DIMETHYL-2-NORBORNANEMETHANOL

Reaction: ##STR174## Procedure:

Into a 3 liter reaction flask fitted with a stirrer, reflux condenser,thermometer, dropping funnel and a N₂ bleed, is added 55 g of magnesiumturnings (2.26 moles) and 1 liter of anhydrous tetrahydrofuran. Theapparatus is blanketed with dry N₂, and 2 moles of allyl chloride (152g, 162 ml) is placed in the addition funnel; about 10 cc is added atonce with stirring. When the reaction begins (exotherm to 30°), theflask and contents are cooled to 0° C (dry ice/isopropyl alcohol bath)and the remainder of the allyl chloride is added over a 3 hour periodwhile the temperature is kept at 0°-5°. When addition is complete thecontents of the flask are stirred for an additional hour while warmingto 22° C at room temperature. The Grignard solution is decanted from theexcess magnesium into another reaction flask and 330 g of a solution of3,3-dimethyl-2-norbornanecarboxaldehyde in benzene prepared as inExample I (62% aldehyde by GLC area normalization) is added over onehour. The reaction is exothermic and the temperature rises until thesolution refluxes (65-70° C). At the end of the addition, the mixture isheated and refluxed for an additional 1/2 hour. The Grignard complex ishydrolyzed by the addition of about 400 cc of 15% HCl (to a pH of 1).The aqueous layer is separated and extracted with 200 cc of benzene. Thecombined organic layers are stripped on a rotary evaporator and theresidue is distilled through a 1' stone packed column after addingthereto 30 g of Primol.sup.®, at 70-77° C at 0.2-0.25 mm Hg pressure,yielding 206 grams product. The resulting product is essentially onepeak by GLC analysis (conditions: 10 foot × 1/8 inch SE-30 column,programmed at 80-220° C at 8°/min.). This corresponds to a yield of 92%theory based on 3,3-dimethyl-2-norbornanecarboxaldehyde added. This peakconsists of a compound having the structure:

    ______________________________________                                         ##STR175##                                                                   NMR Data:                                                                     ______________________________________                                        0.92 ppm   singlets, methyl protons                                                                        (3H each)                                        0.98                                                                          1.0-2.4    complex signals                                                    4.85-5.20  multiplet, CHCH.sub.2                                                                           2H                                               5.68-6.08  multiplet, CHCH.sub.2                                                                           1H                                               ______________________________________                                    

mass spectral data:

m/e = 69, 55, 41, 111, 67, 109

Infrared data:

cm⁻¹ 3475 (--OH), 3079 (--CH═CH₂)

The NMR spectrum is set forth in FIG. 1.

The Infrared spectrum is set forth in FIG. 2.

EXAMPLE III PREPARATION OF 2-(3-BUTENOYL)-3,3-DIMETHYLNORBORNANE USING ASODIUM DICHROMATE-SULFURIC ACID-BENZENE OXIDIZING SYSTEM

Reaction: ##STR176## Procedure:

Sulfuric acid (60 cc, 110 g) is added slowly to 300 ml water withstirring. When the solution cools to room temperature, 300 cc (263 g) ofbenzene and 50 g of alpha-allyl-3,3-dimethyl-2-norbornanemethanol isadded. The mixture is stirred at room temperature and 20 g of sodiumdichromate is added. After one hour a second 20 g portion is added.After an additional one hour of stirring the layers are separated. Thebenzene layer is washed with saturated NaHCO₃ solution and then withwater. The solvent is stripped and the residue is distilled rapidly toyield two distillation fractions. The first distillation fraction has aboiling point range of 65-97° C at 1.2 mm and weighs 2.5 g. The seconddistillation fraction has a boiling point range of 97-99° C at 1.0 mm Hgand weighs 39.4 grams, corresponding to a yield of 80% of theory.

The second distillation fraction is primarily a compound having thestructure: ##STR177##

This compound is purified by means of column chromatography on a columnof silicic acid (deactivated by the addition of 5% water). The compoundis eluted with a mixture of 2% diethyl ether in isopentane. Thus, from1.5 grams of this second distillation fraction was obtained, aftersolvent stripping, 1.0 grams of an oil which was distilled on a microdistillation apparatus, yielding pure2-(3-butenoyl)-3,3-dimethylnorbornane (i), having the following spectralcharacteristics:

    ______________________________________                                        (i) Structure:                                                                 ##STR178##                                                                   NMR data:                                                                     δ, ppm         Interpretation                                           ______________________________________                                        0.95                                                                          1.0                      methyl singlets                                      1.18                     (endo and exo isomers)                               1.24                                                                          1.0-2.5                  complex signals                                       3.12                                                                                   ##STR179##      doublet of quartets                                 6.1                                                                                    CH.sub.2CHCH.sub.2                                                                            multiplets                                           6.9                                                                           ______________________________________                                    

Mass Spectral Data:

m/e = 123, 41, 67, 81, 39, 151

Infrared Data:

cm⁻¹ 1720 (normal carbonyl)

The NMR spectrum for this compound is set forth in FIG. 5. The Infraredspectrum is set forth in FIG. 6.

When either crude or purified 2-(3-butenoyl)-3,3-dimethylnorbornane issubjected to GLC analysis, a second material is observed. This materialis trapped and identified as cis-2-(3-butenoyl)-3,3-dimethylnorbornane(ii), having the following spectral characteristics:

    ______________________________________                                        (ii) Structure:                                                                ##STR180##                                                                   NMR data:                                                                     δ, ppm             Interpretation                                       ______________________________________                                        0.85                                                                          0.96                     methyl singlets                                      1.20                     (endo and exo isomers)                               1.24                                                                          1.88                                                                                      ##STR181##   doublet of triplets                                  1.0 - 2.5                complex signals                                      6.12                                                                                      ##STR182##   multiplets                                           6.76                                                                          ______________________________________                                    

Mass Spectral Data:

m/e = 41, 69, 125, 67, 81, 108, 123

Infrared Datum:

cm⁻¹ 1685 (conjugated carbonyl)

The NMR spectrum is set forth in FIG. 3. The Infrared spectrum is setforth in FIG. 4.

EXAMPLES IV-X OXIDATION AND ATTEMPTED OXIDATION OFALPHA-ALLYL-3,3-DIMETHYL-2-NORBORNANEMETHANOL

Using different oxidizing agents, the following Examples, as set forthin Table I, are performed with the results indicated whereby2-(3-butenoyl)-3,3-dimethylnorbornane is produced in a number ofreactions and is not produced where "no reaction" is indicated:

                  TABLE I                                                         ______________________________________                                             Quantity                                                                 Ex.  of Alcohol                                                                              Oxidizing Agent and                                            No.  Reactant   Conditions     Result                                         ______________________________________                                        IV                 Jones Reagent at room                                                                       Mixture of                                                      temperature.  many products                                                                 formed. -V 50 g Na.sub.2 Cr.sub.2                                             O.sub.7 (40 g)/H.sub.2 SO.sub.4 Successfu                                     l oxid-                                                         (60 cc)/benzene                                                                             ations; 50% con-                                                (300 cc) ; room temp-                                                                       version to ketone.                                              erature for 2 hours.                                       VI   1     g       10 ml dimethyl sul-                                                                         No reaction.                                                    foxide/5 g acetic                                                             anhydride at 60° C.                                 VII  10    g       Copper chromite (1 g)/                                                                      No reaction.                                                    200° C for 1 hour.                                  VIII 5     g       Pyridinium chloro-                                                                          50% conversion                                                  chromate (8.5 g)                                                                            to ketone.                                                      (prepared according                                                           to Corey, Tetrahedron                                                         Letters, 31, 2647,                                                            1975); methylene                                                              dichloride (50 cc);                                                           room temperature; 1                                                           hour.                                                      IX   5     g       Chromium trioxide                                                                           50% conversion                                                  (2.5 g)/acetic acid                                                                         to ketone.                                                      (5 ml)/water (50 ml);                                                         room temperature; 1                                                           hour.                                                      X    15    g       Jones reagent (25 ml)                                                                       90% conversion                                                  (prepared according                                                                         to ketone.                                                      to Example IV)/acetone                                                        (15 ml), -5° C, 2 hours.                            ______________________________________                                    

EXAMPLE XI PREPARATOON OFENDO-2-(TRANS-2-BUTENOYL)-3,3-DIMETHYL-5-NORBORNENE

Reaction: ##STR183##

Into a three necked flask equipped with a condenser, thermometer,mechanical stirrer and cooling bath (dry-ice-isopropyl alcohol) ischarged 666 grams (3.0 moles) of 3M methylmagnesium chloride intetrahydrofuran. To this is added a solution of 321 grams (3.0 moles) ofmethyl aniline in 300 ml of benzene over a 30 minute period, keeping thereaction temperature at 20-30° C. The reaction is exothermic and methanegas is evolved. When the gas evolution ceases a solution of 510 g (3.0moles) of endo-2-acetyl-3,3-dimethyl-5-norbornene (prepared by AlCl₃catalyzed reaction of cyclopentadiene and mesityl oxide, U.S. Pat. No.3,852,358) in 300 ml of benzene is added over 40 minutes with thetemperature kept at 20-30° C. The mixture is stirred at room temperaturefor one hour and then cooled to 0° C. At this temperature 132 g (3.0moles) of acetaldehyde in 300 ml of benzene is added over 30 minutes.After an additional 30 minutes at 0° C, 600 g of 37% HCl diluted with1200 ml of water is added. After another 15 minutes at 0° C the layersare separated. The organic layer is washed twice with water and driedover MgSO₄. The solvent is evaporated keeping the liquid temperaturebelow 45° C. The residue is then combined with 600 ml of aceticanhydride and 150 g of sodium acetate, stirred and heated to 100° C for2 hours. The mixture is cooled to 80° C and water is added to destroyexcess acetic anhydride. The mixture is cooled, washed with water,saturated NaHCO₃ solution and dried over MgSO₄. The product is distilledwithout fractionation to give 204 g of an oil, b.p. 70-130° C (1.0-1.5mm). This material contained about 50% starting ketone and a mixture ofreaction products. The major reaction product is isolated byredistillation followed by preparative GLC on a 6 foot × 1/4inch columnpacked with 10% Carbowax 20M. On the basis of its NMR spectrum theproduct is predominantly the endo isomer (>90%): ##STR184##

The NMR spectrum is set forth in FIG. 7. The Infrared spectrum is setforth in FIG. 8.

EXAMPLE XII PREPRATION OF 2-(2-BUTENOYL)-3,3-DIMETHYLNORBORNANE(PRIMARILY THE "TRANS" ISOMER)

Reaction: ##STR185##

Into a 2 liter autoclave the following materials areplaced:______________________________________IngredientsQuantity______________________________________2-acetyl-3,3-dimethyl-norbornane644 g (4 moles)acetaldehyde 132 g (3 moles)boron oxide 105 g (1.5moles)boric acid 12 g (0.2 moles)______________________________________

The autoclave is sealed and the contents are heated at 150° C for aperiod of 3 hours at autogeneous pressure. At the end of the 3 hoursperiod the contents of the autoclave are cooled at room temperature andfiltered. The filter cake is washed with 250 ml cyclohexane and thefiltrate is distilled rapidly through a 2 inch column, after addingthereto 20 g Primol.sup.® and 0.1 g Ionox.sup.® to give 649 g of oilcollected at 77-129° C and a pressure of 2.7-4.0 mm Hg. This material isthen fractionally distilled on a 12 inch × 1 inch Goodloe column, afteradding thereto Primol.sup.® and Ionox.sup.®, to give 490 g of oilcollected at 73-78° C and a pressure of 3.34-4 mm Hg. The resultingmaterial, insofar as its fragrance properties are concerned, has asweet, woody, fruity, spicey and herbaceous aroma with pine needlenuances. insofar as flavor characteristics are concerned, this materialhas a fruity, pine needle/green, winey aroma with a piney,eugenol/clove, spicey, fruity, and winey flavor.

NMR, Infrared and Mass Spectral analyses confirm that the resultingstructure is:______________________________________ ##STR186##NMRdata:δ, ppm Interpretation______________________________________0.82singlets, methyl protons0.93 (endo and exo isomers)1.161.201.28 CHCH₃doublet of doublets1.0-2.5 complex signals6.1 6.7 ##STR187## multiplets1H each______________________________________

Mass Spectral Data:

m/e = 69, 41, 125, 39, 67, 108

Infrared Data:

cm⁻¹ 1690 (conjugated carbonyl)

The NMR spectrum is set forth in FIG. 9. The Infrared spectrum is setforth in FIG. 10.

EXAMPLE XIII PREPARATION OF 2-(2-BUTENOYL)-3,3-DIMETHYLNORBORNANE

Reaction: ##STR188##

Into a 2 liter autoclave the following materials are placed:

    ______________________________________                                        Ingredients         Quantity                                                  ______________________________________                                        2-acetyl-3,3-dimethyl-                                                        norbornane          830 g (5 moles)                                           acetaldehyde        88 g (2 moles)                                            boron oxide         50 g (0.71 moles)                                         ______________________________________                                    

The autoclave is sealed and the contents thereof are heated to 170-185°C and maintained at that temperature for two hours during which time thepressure within the autoclave is 50 psig. At the end of the two hourperiod the rection mass is cooled to room temperature and decanted, andthe resulting liquid, after adding thereto 20 g Primol.sup.® and 0.1 gIonox.sup.®, is distilled rapidly through a 2 inch column, to yield 625g of crude material collected at 77-129° C and a pressure of 2.7-4.0 mmHg. The resulting material, after adding thereto Primol.sup.® andIonox.sup.®, this then fractionally distilled through a 12 inch × 1inchGoodloe column at 73-78° C and a pressure of 3.3-4mm Hg. The major peakis trapped on a GLC column yielding a material having the structure:##STR189## as confirmed by GLC, IR and NMR analyses.

The material has a fruity aroma with piney and musty nuances insofar asits fragrance properties are concerned and a fruity and berry aroma withwaxy, berry, sour and bitter flavor characteristics infsofar as itstaste properties are concerned.

EXAMPLE XIV BLUEBERRY FLAVOR FORMULATION

The followig formulation isprepared:______________________________________Ingredients Parts byWeight______________________________________Heliotropin 3.0Terpinenol-4(10% in 95% aqueous food grade ethanol) 0.2Benzaldehyde 1.5Anisaldehyde0.2Phenyl acetaldehyde 0.4Benzyl formate 0.5Benzyl acetate2.0Cis-3-hexenyl benzoate (10% in 95% aqueous food grade ethanol)0.5Methyl hexanoate 2.0Hexanal 1.0Eucalyptol (1% in 95% aqueous foodgrade ethanol) 0.5Eugenol 0.2Acetaldehyde 3.0Ethyl acetate 21.0Ethylbutyrate 26.0Propylene glycol 38.0100.0______________________________________

The above formulation is split into 2 portions. To the first portion isadded, at the rate of 1%, 2-(2-butenoyl)-3,3-dimethylnorbornane. Thesecond portion contains nothing added thereto. Both formulations, withand without the said 2-(2-butenoyl)-3,3-dimethylnorbornane (producedaccording to Example XII), are combined with water at the rate of 100ppm. The flavor with the 2-(2-butenoyl)-3,3-dimethylnorbornane, preparedaccording to Example XII, has a more winey, fruity, piney character andis closely similar to the flavor of wild blueberries. It is thereforeprepared to the basic blueberry formulation which does not contain said2-(2-butenoyl)-3,3-dimethylnorbornane.

EXAMPLE XV PINE NEEDLE OIL FORMULATION

The following formulation isprepared:______________________________________Ingredients Parts byWeight______________________________________Turpentine gum oil100Limonene 70Gum camphor 10Isobornyl acetate 50Borneol302-(2-Butenoyl)-3,3-dimethylnorbornane(produced according to ExampleXII) 40Mixture of 2-(3-butenoyl)-3,3-dimethyl-norbornane and2-(2-butenoyl)-3,3-dimethylnorbornane (producedaccording to the processofExample III 100Alpha-allyl-3,3-dimethyl-2-norbornane-methanol(produced according to theprocess of Example II)70______________________________________

The 2-(2-butenoyl)-3,3-dimethylnorbornane produced according to ExampleXII imparts a green, melony, herbal, ozoney and twiggy character of pineneedle to the middle portion of the aroma profile and dry out.

The mixture of 2-(2-butenoyl)-3,3-dimethylnorbornane and2-(3-butenoyl)-3,3-dimethylnorbornane produced according to Example IIIimparts the sweet, bright, melony, herbal lift so necessary to this pineneedle oil formulation.

The alpha-allyl-3,3-dimethyl-2-norbornanemethanol produced according toExample II imparts the sweet, woody, melony, cut wood note to the dryout aroma of this pine needle oil formulation.

EXAMPLE XVI FLAVOR USE OF ALPHA-ALLYL-3,3-DIMETHYL-2-NORBORNANEMETHANOL

The following basic cinnamon formulation isprepared:______________________________________Ingredients Parts byWeight______________________________________Cinnamic aldehyde 70Eugenol15Cuminic aldehyde 1Furfural 0.5Methyl cinnamate 5.0Cassia oil8.5______________________________________

This formulation is split into two parts. To the first part is added, atthe rate of 5%, alpha-allyl-3,3-dimethyl-2-norbornanemethanol preparedaccording to Example II. To the second part no additive is added. Thealpha-allyl-3,3-dimethyl-2-norbornanemethanol adds a more cinnamonbark-like character in aroma and taste and a more woody/sweet aroma. Itis therefor preferred to the formulation without such additive. Theformulations are compared in water at the rate of 10 ppm.

EXAMPLE XVII PREPARATION OF ALPHA-ETHYL-3,3-DIMETHYL-2-NORBORNANEMETHNOL

Reaction: ##STR190##

Into a 1 liter reaction flask equipped with a stirrer, thermometer,condenser, nitrogen inlet tube and dropping funnel is placed 129 cc of a2.9 molar solution of ethyl magnesium chloride in tetrahydrofuran. Overa 20 minute period 19.0 g of 3,3-dimethyl-2-norbornanecarboxaldehyde isadded with stirring. The reaction is exothermic. The reaction mass isthen refluxed for a period of 3 hours. At the end of the 3 hour periodthe reaction mass is cooled to room temperature, and 100 cc of saturatedammonium chloride solution is added thereto. The organic layer is thenextracted with 500 cc diethyl ether, and the extract is concentrated anddistilled through a micro Vigreux column after adding thereto 3 g ofPrimol.sup.®.

Mass spectral, NMR and infrared analysis of the distilled product, b.p.85° C at 1.5 mm Hg, indicates that it has thestructure:______________________________________ ##STR191##NMR data:δ,ppm Interpretation______________________________________0.96 singletsgem dimethyl1.021.04 triplet CH_(2CH) ₃1.0-2.4 multiplet ##STR192##3.5multiplet ##STR193##______________________________________

mass Spectral Data:

m/e = 67, 41, 121, 81, 59, 182 (parent peak)

From a food flavor standpoint the resulting material has a sweet, woody,minty aroma with camphoraceous, green and earthy nuances and a woody,green, minty flavor with spicey, earthy, cooling, red beet-like andcamphoraceous nuances at 5 ppm. From a perfumery standpoint theresulting material has a musty, sweet, fruity, woody aroma with anartemesia character.

This material has a significant utility in tobacco filter flavors whereit lends a cooling effect with sweet, woody, and piney notes both priorto and during smoking, when 10 micro liters of a 10% solution is addedto the filter.

The NMR spectrum is set forth in FIG. 11.

The Infrared spectrum is set forth in FIG. 12.

EXAMPLE XVIII USE OF ALPHA-ETHYL-3,3-DIMETHYL-2-NORBORNANEMETHANOL

The following basic raspberry formulation is prepared:

    ______________________________________                                        Ingredients             Parts by Weight                                       ______________________________________                                        Vanillan                2                                                     Maltol                  4                                                     Parahydroxy benzyl acetone                                                                            5                                                     Dimethyl sulfide        1                                                     Alpha-ionone (10% in propylene glycol)                                                                2                                                     Ethyl butyrate          6                                                     Ethyl acetate           16                                                    Isobutyl acetate        14                                                    Acetic acid             10                                                    Acetaldehyde            10                                                    Propylene glycol        930                                                                           1000                                                  ______________________________________                                    

The above formulation is split into two parts. To the first part, at therate of 0.3% is added alpha-ethyl-3,3-dimethyl-2-norbornanemethanolproduced according to Example XVII. No additive is added to the secondpart. The two formulations are compared in water at the rate of 50 ppm.The flavor containing the alpha-ethyl-3,3-dimethyl-2-norbornanemethanolhas a more ripe raspberry taste and a woody, raspberry kernel character.Therefore, the raspberry formulation containing the norbornanederivative as an additive has a more natural like and morecharacteristic raspberry flavor and is therefor preferred.

EXAMPLE XIX PREPARATION OFALPHA-METHALLYL-3,3-DIMETHYL-2-NORBORNANEMETHANOL

Reaction: ##STR194##

Into a 3 liter reaction flask equipped with a stirrer, condenser,nitrogen inlet tube, thermometer and dropping funnel are placed 24 g ofmagnesium with just enough tetrahydrofuran to cover it. Two milliliters(approximately 20 cc) of methallyl chloride is then added to start thereaction. When the reaction is well under way, 500 cc of tetrahydrofuranis added, and 90.5 g of methallyl chloride is added dropwise over aperiod of 2 hours while maintaining a steady reflux. After the finaladdition, refluxing is continued for a period of one hour. Fifty gramsof norbornane aldehyde, produced according to Example I, dissolved in100 cc of toluene is then added over a period of 20 minutes, and thereaction mass is again refluxed for a period of 3 hours. The reactionmass is then cooled to room temperature, and 100 cc of saturated aqueousammonium chloride solution is then added thereto. The reaction mass isthen extracted with diethyl ether and the diethyl ether extract isconcentrated. The concentrate is then distilled on an 8 inch × 1 1/2inches porcelain saddle packed column after adding thereto 5 g of Primol®.

The distilled product, b.p. 100° C at 2.0 mm Hg, is subjected to NMR,IR, Mass Spectral and UV analyses confirming that the structureis:______________________________________ ##STR195##NMR data:δ, ppmInterpretation______________________________________0.94 singlets gemdimethyl1.01.77 singlet ##STR196##1.0-2.4 multiplet ##STR197##4.72multiplet ##STR198##______________________________________

mass Spectral Data:

m/e = 69, 41, 55, 43, 69, 208 (parent peak).

The resulting material has a musty, sweet, woody, minty aroma with anintense, fresh cut pine/spruce nuance.

The NMR spectrum is set forth in FIG. 13.

The Infrared spectrum is set forth in FIG. 14.

EXAMPLE XX PREPARATION OF2-(4'-METHYL2'-PENTENOYL)-3,3-DIMETHYLNORBORANE

Reaction: ##STR199##

Into a 3 liter reaction flask equipped with a stirrer, thermometer,reflux condenser, addition funnel and nitrogen inlet tube the followingmaterials are added:

    ______________________________________                                        Ingredient            Amount                                                  ______________________________________                                        methanol              500 g                                                   potassium hydroxide   56 g                                                    toluene               50 g                                                    2-acetyl-3,3-dimethyl-                                                        norbornane            500 g                                                   ______________________________________                                    

The reaction mass is heated to reflux for a period of 1 hour at whichtime 240 g (3.3 moles) of isobutyraldehyde is added over a period of 20minutes. When the addition is complete, the reaction mass is stirred foran additional 4 hours at a temperature of 72° C. At the end of the fourhour period, 50 g of concentrated HCl is added to the reaction mass. Thereaction mass is then admixed with 1 liter of water and 500 ml oftoluene. The aqueous phase is then extracted with one 250 ml portion oftoluene, and the toluene is combined with the organic layer which iswashed as follows:

Two 250 ml portions of water;

one 500 ml portion of 5% sodium bicarbonate solution; and

one 250 ml portion of saturated sodium chloride solution.

The crude material is then stripped of solvent using a Buchi evaporator,and the stripped crude (after adding thereto 25 g Primol.sup.® and 1 gIonox.sup.®) is rapidly distilled using a 2 inch column. The distilledmaterial is then fractionated on a 12 inch Goodloe packed column afteradding thereto 30 g Primol.sup.® and 1 g Ionox.sup.®.

GLC, NMR, Infrared and Mass Spectral analyses yield the information thatthe resulting material is a mixture of three compounds having thestructures: ##STR200##

The GLC profile is set forth in FIG. 15.

The NMR spectrum for the mixture of compounds having the structures:##STR201## is set forth in FIG. 16. The Infrared spectrum is set forthin FIG. 17.

The NMR spectrum for the mixture of ketones having the structures:##STR202## is set forth in FIG. 18. The Infrared spectrum for thismixture of ketones is set forth in FIG. 19.

The NMR spectrum for the compound having the structure: ##STR203## isset forth in FIG. 20. The Infrared spectrum for this keto-ether compoundis set forth in FIG. 21.

Structural Assignments______________________________________I. Mixtureof A and BInfrared Data: 1618 cm⁻¹, 1705, 1698NMR Data (CDCl₃):ppmInterpretation______________________________________6.70 doublet ofdoublets (J ≈ 16 Hz, 7 Hz) ##STR204##6.00 doublet of doublets (J ≈ 6 Hz,1 Hz) ##STR205##5.28 broad triplet (J ≈ 6 Hz) ##STR206##3.03 broaddoublet (J ≈ 6 Hz) ##STR207##1.74 1.63 broad singlets ##STR208##1.23,0.87, 0.83 singlets ##STR209##1.07 doublet (J ≈ 6 Hz)##STR210##______________________________________

comparison of the integrals for the signals at 6.70 and 6.00 ppm withthe signal at 5.28 ppm shows that the ratio of A/B is approximately 1/1.

II. Compound C

    ______________________________________                                        II. Compound C                                                                NMR Data:                                                                     ppm              Interpretation                                               ______________________________________                                        3.50     1H multiplet                                                                               ##STR211##                                              3.34, 3.31                                                                             3H two singlets                                                                            ##STR212##                                              1.24 0.85                                                                              3H singlet 3H singlet                                                                      ##STR213##                                              0.89     6H doublet (J≈5 Hz)                                                                ##STR214##                                              ______________________________________                                    

infrared Datum:

1705 cm⁻¹

The overall mixture of the three compounds in Fraction 12, from a foodflavor standpoint, has a fruity, raspberry, sweet aroma with a greennuance and a fruity, raspberry, green flavor with a bitter nuance at 5ppm. The mixture of ketones A and B, from a perfumery standpoint, has along lasting fruity, berry-like aroma with chocolate, spicey, winey,sweet, balsamic, fruity, pineapple, raspberry, cinammon, ionone-like,musty, floral, woody, salicyl and amyris nuances. When used with tobaccoit has a sweet, fruity, raspberry-like, green aroma prior to smoking,and adds a sweet, fruity, green taste to the tobacco smoke flavor whenused at 200- 500 ppm levels in tobacco.

EXAMPLE XXI PREPARATION OF2-(4'-METHYL-2'-METHYL-2'-PENTENOYL)-3,3-DIMETHYL-5-NORBORNENE

Reaction: ##STR215##

Into a 3 liter reaction flask equipped with a stirrer, thermometer,reflux condenser and addition funnel are placed solution of 56 g ofpotassium hydroxide in 500 g of methanol. While maintaining themethanol/KOH solution at 1-4° C, a solution of 500 g (3 moles) of2-acetyl-3,3-dimethyl-5-norbornene, 240 g (3.3 moles) ofisobutyraldehyde, and 50 g of toluene is added from the addition funnelover a period of 35 minutes.

The reaction mass is then stirred for a period of one hour at 2-4° C andfor a period of 12 hours at 71° C to 73° C, while refluxing. Thereaction mass is then cooled and transferred to a separatory funnel andmixed with 1 liter of water and 500 ml toluene. The aqueous layer isseparated and extracted with one 250 ml portion of toluene. The organiclayer is combined with the toluene extract and is washed with:

one 500 ml portion of water;

one 500 ml portion of 5% sodium bicarbonate solution; and

one 500 ml portion of saturated aqueous sodium chloride solution.

The crude organic material is then stripped of solvent and distilledrapidly after thereto 25 g Primol.sup. ® and 1 gram Ionol.sup. ®.

The distilled material is then fractionally distilled on a 12 inchesGoodloe column.

GLC, IR, NMR and Mass Spectral analyses yield the information that theresulting material is a mixture of 3 compounds having the structures:##STR216##

The GLC profile for this mixture is set forth in FIG. 22.

The product, from a food flavor standpoint, has a sweet, red berryjam-like, fruity aroma with citrus, ionone-like, berry, pine-needle andpungent nuances and a fruity, red berry jam flavor with green, freshraspbery and piney nuances.

From a perfumery standoint this material has a fruity, berry-like aroma.In tobacco, prior to smoking, this material has a sweet, floral-like,green aroma. On smoking, sweet, fruity and slightly floral nuances arecreated.

The three materials produced are separated in a GLC column (conditions:5 foot × 1/4 inch 5% SE-30 column operated at 200° C isothermal).

The NMR spectrum for the mixture of compounds having the structures:##STR217##

Spectral Data for Total Mixture

Infrared Data:

1620 ^(cm-1), 1705, 1685, 1660

    ______________________________________                                        NMR Data:                                                                     ppm                Interpretation                                             ______________________________________                                        6.74     doublet of doublets (J ≈ 16 Hz, 7 Hz)                                                ##STR218##                                            5.95-6.50                                                                              multiplet                                                                                    ##STR219##                                                                    ##STR220##                                            5.34     broad triplet                                                                                ##STR221##                                            1.78 1.66                                                                              broad singlets                                                                               ##STR222##                                            1.13, 1.04, 0.81, 0.79                                                                 singlets                                                                                     ##STR223##                                            1.03     doublet (J ≈ 6 Hz)                                                                   ##STR224##                                            3.80 3.40                                                                              singlets                                                                                     ##STR225##                                            ______________________________________                                    

EXAMPLE XXII PREPARATION OF 2-(1-HYDROXBUTYL)-3,3-DIMETHYLNORBORNANE AND2-BUTYRYL-3,3-DIMETHYLNORBORNANE

Reaction: ##STR226##

PART A

Into a 200 cc flask equipped with a stirrer, thermometer and refluxcondenser is placed 15 g of dimethylnporbornanecarboxaldehyde, producedaccording to the process of Example I, and 50 cc diethyl ether. Over a15 minute period 50 cc of a solution of n-propyl magnesium chloride (2.2molar in diethyl ether) is added to the aldehyde. The reaction mass isthen refluxed for a period of 1/2 hour whereupon a GLC analysisindicated complete reaction of the norbornanecarboxaldehyde. Theresulting reaction mass is then hydrolyzed with saturated aqueousammonium chloride solution, and water is then added to dissolve thesalts. The water phase is extracted with 50 cc of diethyl ether, and theether extract is combined with the organic phase and stripped. Theproduct is distilled on a micro Vigreux column yielding 13.3 grams in 5fractions, b.p. 79-82° C at 1 mm Hg.

    ______________________________________                                        NMR Data:                                                                     δ, ppm   Interpretation                                                 ______________________________________                                        0.88                                                                          1.02               singlets, gem dimethyl                                     1.01               protons (2 sets; 2 isomers                                 1.25               exo and endo)                                              1.06 triplet       CH.sub.3CH.sub.2                                           2.34-1.32          methylene and methine                                                         protons                                                    3.56 multiplet                                                                                    ##STR227##                                                1.13 singlet       OH                                                         ______________________________________                                    

infrared Data:

950, 1005, 1055, 1100, 1355, 1375, 1455, 2860, 2920, 2950, 3360 cm⁻¹

Mass Spectral Data:

m/3 = 41, 135, 55, 67, 43, 27; parent peak=196

The NMR spectrum is set forth in FIG. 25. The Infrared spectrum is setforth in FIG. 26.

PART B

A 2.5 g portion of the distillate produced in Part A is dissolved in 10cc of acetone and the resulting solution is cooled to 0-5° C while a"Jones Reagent" prepared according to Example IV is added dropwise (2 mltotal required). GLC analysis indicates one product is formed. 25 cc ofwater is added to the reaction mass, and the aqueous phase is extractedwith diethyl ether. The diethyl ether extract and the organic phase arecombined and washed with saturated sodium chloride solution. The washeedorgannic solution is stripped and distilled on a micro Vigreux columnyielding 1.3 grams of product, distilling at 90° C and 1.0 mm Hgpressure.

NMR, IR and Mass Spectral analyses confirm that the compound is2-butyryl-3,3-dimethylnorbornane.

    ______________________________________                                        NMR Data:                                                                     δ, ppm   Interpretation                                                 ______________________________________                                        0.84                                                                          0.90                                                                          0.95           CH.sub.2 CH.sub.3 ;CH.sub.3 ; endo and                         1.14           exo isomers                                                    1.31                                                                          1.0-1.06       multiplets                                                     2.3 triplet                                                                                   ##STR228##                                                    ______________________________________                                    

infrared Datum:

1700 cm⁻¹ (C═O)

Mass Spectral Data:

m/e = 123, 43, 41, 127, 27, 67; parent peak = 194

the NMR spectrum is set forth in FIG. 27. The Infrared spectrum is setforth in FIG. 28.

EXAMPLE XXIII PREPARATION OF 2-BUTYROYL-3,3-DIMETHYLNORBORNANE

Reaction: ##STR229##

Into a 250 cc Parr shaker the following materials are placed:

    ______________________________________                                        Ingredient            Quantity                                                ______________________________________                                        2-(trans-2-butenoyl)-3,3-                                                     dimethylnorbornane                                                            prepared according to                                                         the process of Example                                                        XII                   90 g                                                    5% palladium-on-carbon                                                        catalyst               1 g                                                    ______________________________________                                    

The Parr shaker is sealed and then pressurized up to 50 psig withhydrogen and periodically repressurized over a period of 7 hours tomaintain a pressure of 50 psig. During this period of time thetemperature of the reaction mass remains at 25° C. At the end of the 7hour period the Parr shaker is opened and the contents removed andfiltered. To the filtrate, 5.0 g of Primol.sup. ® and 0.1 g ofIonol.sup. ® is added. The resulting mixture is then distilled on a fourfoot Vigreux column to give 47 g of oil, b.p. 93-95° C at 3.0 mm Hg.

NMR, IR and Mass Spectral analyses yield the information that theproduct has the structure:______________________________________##STR230##NMR Data:δ, ppmAssignments______________________________________0.850.96 singlets, 2sets,1.14 (2 isomers)1.220.89 (t) CH_(3CH) ₂2.08-1.46 methylene andmethine protons2.30 diffuse triplet protons alphacarbonyl______________________________________

Infrared Data:

1100, 1115, 1290, 1360, 1400, 1455, 1700, 2870, 2940 cm⁻¹

Mass Spectral Data:

m/e = 123, 41, 43, 127, 27, 151; parent peak = 194

The NMR spectrum is set forth in FIG. 29. The Infrared spectrum is setforth in FIG. 30.

EXAMPLE XXIV PREPARATION OF 2-(4'-PENTENOYL)-3,3-DIMETHYLNORBORNANE

Reaction: ##STR231##

Into a 500 ml reaction flask equipped with a stirrer, thermometer,reflux condenser, addition funnel and nitrogen inlet tube is placed asuspension of 48 g of 55% sodium hydride and 250 ml toluene. Under anitrogen blanket, 166 g (1 mole) of 2-acetyl-3,3-dimethylnorbornane isadded over a period of 5 minutes. The resulting mixture is heated toreflux for a period of 70 minutes and then is cooled to 45° C. Allylchloride (76 g, 1 mole) and 4 g of tricapryl methyl ammonium chloride(Aliquat 336.sup.®, produced by General Mills Chemical Inc.) is addedthereto over a period of 15 minutes. The reaction mass is then stirredat 60° C for a period of 12 hours.

The resulting suspension is allowed to settle, and the reaction mass isfiltered through glass wool. The filtrate is washed with water, and thesolvent is removed on a rotary evaporator to yield a white milky oil.GLC analysis indicates three peaks. The GLC profile (conditions: 8 foot× 1/4 inch SE-30 column, programmed at 200° C isothermal; 40 ml/minute)is set forth in FIG. 31. NMR, IR and Mass Spectral analyses confirm thatthe 3 compounds produced have the following structures: ##STR232##

The compound having the structure: ##STR233## has the following massspectral data: m/e = 123, 81, 67, 55, 151, 108, 83; parent peak=206

The NMR data for this compound is as follows:

    ______________________________________                                        δ, ppm       Interpretation                                             ______________________________________                                        0.88   singlet                                                                                   gem dimethyl group                                         1.22   singlet                                                                4.92                                                                          5.05               --CH=CH.sub.2                                              5.12                                                                          5.65-5.95          --CH.sub.2 --CH=CH.sub.2                                   ______________________________________                                    

The NMR spectrum is set forth in FIG. 32.

The compound having the structure: ##STR234## has the following NMRanalysis:______________________________________δ, ppmInterpretation______________________________________1.04 singlet gemdimethyl group1.02 singlet2.05 singlet ##STR235##2.40 J=7Hz doubletCH_(2CHCH) ₂4.92 multiplet CHCH₂5.96 multiplet5.3-5.8 multipletCH_(2CHCH) ₂______________________________________

the NMR spectrum for this compound is set forth in FIG. 33.

The compound having the structure: ##STR236## has the following NMRdata:

    ______________________________________                                        δ, ppm       Interpretation                                             ______________________________________                                        0.88 singlet                                                                                     gem dimethyl group                                         1.20 singlet                                                                  4.92-5.14 multiplet                                                                              CHCH.sub.2                                                 5.5-5.9 multiplet  CHCH.sub.2                                                 ______________________________________                                    

The NMR spectrum is set forth in FIG. 34. The Infrared spectrum is setforth in FIG. 35. The Infrared data is as follows:

1700 cm⁻¹ (C═O); 1635 cm⁻¹ (C═C)

From a perfumery standpoint, the product has a camphoraceous, woody,fruity (orange) aroma with green and piney undertones.

A process similar to that carried out above is carried out with theexception that instead of sodium hydride, a molar equivalent of sodiumhydroxide is used. The results are that the same three compounds areproduced in the following percentages and in the followingratios:______________________________________Structure PercentRatio______________________________________ ##STR237## 24 1.3 ##STR238##19 1 ##STR239## 57 3

EXAMPLE XXV PRODUCTION OF 2-(4'-PENTENOYL)-3,3-DIMETHYLNORBORNANE

    ______________________________________                                        Part A Reaction:                                                               ##STR240##                                                                    ##STR241##                                                                   Part B Reaction:                                                               ##STR242##                                                                    ##STR243##                                                                   ______________________________________                                    

part A

Into a 3 liter reaction flask equipped with a nitrogen inlet tube,thermometer, reflux condenser and stirrer the following materials areplaced:

sodium hydride (55%): 88 g

diethyl carbonate: 236 g

benzene: 1 liter

Under a nitrogen blanket the resulting mixture is heated to reflux.

Over a period of 30 minutes, 2-acetyl-3,3-dimethylnorbornane is added tothe reaction mass. At the end of the addition, the reaction mass isrefluxed for an additional 40 minutes. Two hundred milliliters of aceticacid followed by 1 liter of water are added to the reaction mass. Theorganic phase is separated, and the resulting crude material isdistilled rapidly using a 2 inch splash column to give 205 g of oil,b.p. 80-160° C at 1 mm Hg.

After 5 g of Primol.sup.® is added to the distilled material, it isfractionally distilled on a 12 inch × 1 inch Goodloe distillation columnto give 119 g of product, b.p. 109-127° C at 1.2 mm Hg.

The distilled material is confirmed by NMR analysis to have thestructure:

    ______________________________________                                         ##STR244##                                                                   NMR Data:                                                                     δ, ppm       Interpretation                                             ______________________________________                                        0.92 singlet                                                                                     gem dimethyl group                                         1.22 singlet                                                                  1.24 (J=7Hz) triplet                                                                             CH.sub.2 CH.sub.3                                          3.35 singlet                                                                                      ##STR245##                                                4.18 (J=7Hz) quartet                                                                             OCH.sub.2 CH.sub.3                                         ______________________________________                                    

the NMR spectrum is set forth in FIG. 36. The Infrared spectrum is setforth in FIG. 37.

    ______________________________________                                        Infrared Data:                                                                1650 CC (m)                                                                   1700 CO (strong)                                                               ##STR246##                                                                   ______________________________________                                    

mass Spectral Data:

m/e = 108, 123, 109, 107, 29, 41; parent peak=238

Part B

One hundred grams of toluene are admixed with 24 g (0.55 moles) ofsodium hydride and heated to 60° C in a 500 cc reaction flask equippedwith a stirrer, thermometer and reflux condenser. Over a period of 80minutes the carboethoxy compound produced in Part A is added to thetoluene/sodium hydride mixture. At the end of the addition of theketocarboxylic acid ester compound, a mixture of 38.5 g of allylchloride and 7 g of tricapryl methyl ammonium chloride (Aliquat336.sup.®, produced by General Mills Chemical Inc.) is added over a 20minute period while maintaining the reaction mass at 80° C.

Fifty milliliters of 50% sodium hydroxide solution and 50 ml of water isthen added to the reaction mass, and the resulting mixture is refluxedfor a period of 2 hours. Water (100 ml) is then added to dissolve theresulting precipitate. Then 110 ml of 20% hydrochloric acid is addedwith the evolution of carbon dioxide gas.

The resulting product is then distilled rapidly at 100° C and 2 mm Hgpressure, and the distilled product (after adding thereto 10 g ofPrimol.sup.® and 1 g of Ionox.sup.®) is fractionated to give an oil,b.p. 90° C/1.0 mm Hg.

The product is confirmed by NMR and Infrared analyses to have thestructure: ##STR247##

The NMR spectrum is set forth in FIG. 38.

    ______________________________________                                        NMR Data:                                                                     δ, ppm       Interpretation                                             ______________________________________                                        0.88 singlet                                                                  1.22 singlet       gem dimethyl group                                         4.92-5.12 multiplet                                                                              CHCH.sub.2                                                 5.65-5.95 multiplet                                                                              CH.sub.2CHCH.sub.2                                         ______________________________________                                    

The Infrared spectrum is set forth in FIG. 39.

Infrared Data:

1630 (C═C), 1700 cm⁻¹ (C═O)

EXAMPLE XXVI PREPARATION OF 2-PENTANOYL-3,3-DIMETHYLNORBORNANE

Reaction: ##STR248##

10 g of 2-(4'-pentenoyl)3,3-dimethylnorbornane produced according toPart B of Example XXV and 50 ml of isopropyl alcohol is placed in a Parrshaker along with 0.5 g of palladium catalyst. The Parr shaker is sealedand pressurized with hydrogen up to 30 psig and over a 2 hour period isrepressurized with hydrogen as needed to maintain the pressure at 30psig. During this period of time the temperature of the reaction massremains at 25° C. At the end of the 2 hour period the mass is filtered.The solvent is then evaporated and the product is isolated usingpreparative GLC.

NMR, Mass Spectral and Infrared analyses confirm that the resultingproduct has the structure: ##STR249## This material has a sweet, berry,mandarin orange aroma with pineynuances.______________________________________NMR Data:δ, ppmInterpretation______________________________________1.86 singlet gemdimethyl group -2.24 singlet0.88 (J≈ 6Hz) CH₂ CH₃ triplet2.30 (J≈7Hz)triplet ##STR250##2.30 singlet##STR251##______________________________________

mass Spectral Data:

m/e = 123, 41, 67, 81, 57, 108; parent peak= 208

Infrared Datum:

1700 cm⁻¹ (>C═O)

The NMR spectrum is set forth in FIG. 40. The Infrared spectrum is setforth in FIG. 41.

EXAMPLE XXVII PREPARATION OFALPHA-METHALLYL-ALPHA,3,3-TRIMETHYL-5-NORBORNENE-2-METHANOL

Reaction: ##STR252##

Into a 1 liter reaction flask equipped with a reflux condenser,thermometer, stirrer, dropping funnel and nitrogen inlet tube are placed12 g (0.5 moles) of magnesium turnings and 250 cc anhydrous diethylether. Over a 2 hour period, 45.3 g (0.5 moles) of methallyl chloride isadded. The Grignard solution is stirred for 1/2 hour and 28 g of2-acetyl-3,3-dimethyl-5-norbornene is added over a 20 minute period. Themixture is stirred at reflux for 1/2 hour and then is hydrolyzed by theaddition of saturated ammonium chloride solution. The organic layer iswashed with water and dried over magnesium sulfate. The mixture is thenfiltered and the solvent evaporated to yield 40 g of an oil, which isthen fractionated on a micro Vigreux column after adding thereto 5 gPrimol.sup.® and a trace quantity of Ionox.sup.®.

Mass Spectral, Infrared and NMR analyses confirm that the resultingcompound has the structure:

    ______________________________________                                         ##STR253##                                                                   NMR Data:                                                                     δ, ppm       Interpretation                                             ______________________________________                                        1.40-0.97          methyl protons                                             1.86               CCH.sub.3                                                  2.36-1.48          methylene and methine                                                         protons                                                    4.84-4.78                                                                                         ##STR254##                                                6.24-1.12          olefinic protons of                                                           norbornene ring                                            ______________________________________                                    

Infrared Data:

700, 880, 1080, 1320, 1360, 1450, 2950, 3500 cm⁻¹.

The NMR spectrum is set forth in FIG. 42. The Infrared spectrum is setforth in FIG. 43.

EXAMPLE XXVIII PREPARATION OFALPHA-ALLYL-ALPHA,3,3-TRIMETHYL-2-NORBORNANEMETHANOL

Reaction:

    ______________________________________                                         ##STR255##                                                                    ##STR256##                                                                    ##STR257##                                                                   Ingredient         Quantity                                                   ______________________________________                                        2-acetyl-3,3-dimethyl-                                                        norbornane         28.5 g (0.17 moles)                                        magnesium          12.0 g (0.5 moles)                                         allyl chloride     38.25 g (0.5 moles)                                        anhydrous ether    200 cc                                                     ______________________________________                                    

The magnesium turnings are placed into a 1 liter, 3 neck reaction flask,followed by 200 cc of anhydrous ether. Approximately 6 cc of allylchloride is added to initiate formation of the Grignard reagent. Whenthe reaction is initiated, the remaining allyl chloride is addeddropwise over a 2 hour period, with moderate reflux. After the addition,reflux is continued for 1 hour; at which time 28.5 g2-acetyl-3,3-dimethylnorbornane is introduced over a 20 minute period.The reaction is very exothermic during this addition. At the end of theaddition, refluxing is continued for 1 hour. The work up is carried outby hydrolyzing with NH₄ Cl solution, filtering and separating thelayers. The organic layer is washed with two 200 cc portions of water,dried over MgSO₄, filtered and concentrated to give 34 grams of oilwhich is distilled to give 26 g of product, b.p. 90-105° C at 1-2 mm Hg.

    ______________________________________                                        NMR Data:                                                                     δ, ppm     Assignment                                                   ______________________________________                                         1.06                                                                         1.10                                                                          1.20                                                                                           methyl protons                                               1.24                                                                          1.26                                                                          1.30                                                                          2.18-1.56                                                                                      methylene protons                                            2.32                                                                          5.16-5.00                                                                                       ##STR258##                                                  6.08-5.64        HCCH.sub.2                                                   ______________________________________                                    

infrared Data:

910, 1085, 1160, 1200, 1250, 1300, 1330, 1360, 1385, 1460, 2860, 2940,3070, 3480 cm⁻¹.

The NMR spectrum is set forth in FIG. 44. The Infrared spectrum is setforth in FIG. 45.

EXAMPLE XXIX PREPARATION OFALPHA-ALLYL-ALPHA,3,3-TRIMETHYL-5-NORBORNENE-2-METHANOL

Reaction: ##STR259##

Into a liter 3 necked reaction flask equipped with a stirrer,thermometer, condenser, drying tube and nitrogen inlet are placed thefollowing materials:

    ______________________________________                                        Ingredients       Quantity                                                    ______________________________________                                        2-acetyl-3,3-dimethyl-5-                                                      norbornene        29.2 g (0.17 moles)                                         magnesium         12.0 g (0.5 moles)                                          allyl chloride    38.25 g (0.5 moles)                                         anhydrous ether   200 cc                                                      ______________________________________                                    

This reaction is carried out under the same conditions as the reactionof Example XXVIII. The work up is carried out by hydrolyzing with NH₄ Clsolution, filtering and separating the layers. The organic layer iswashed with two 200 cc portions of water, dried over MgSO₄, filtered andconcentrated to give 37.0 grams of crude product. The crude product isdistilled on a micro Vigreaux column after adding thereto 5 grams ofPrimol.sup.® and a trace quantity of Ionox.sup.® to give 23 of oil, b.p.90-98° C at 1.0-1.6 mm Hg.______________________________________NMRData:δ, ppmInterpretation______________________________________1.38-0.94 methylprotons2.40-1.50 methylene and methine protons5.20-5.00 HCCH₂6.02-5.66HCCH₂6.28-6.04 norbornene olefinicprotons______________________________________

Infrared Data:

710, 910, 995, 1085, 1140, 1250, 1325, 1360, 1460, 1635, 2960, 3060,3470 cm⁻¹.

The NMR spectrum is set forth in FIG. 46. The Infrared spectrum is setforth in FIG. 47.

EXAMPLE XXX PREPARATION OFALPHA-METHALLYL-ALPHA,3,3-TRIMETHYL-2-NORBORNANE-METHANOL

Reaction: ##STR260##

Into a 1 liter 3 necked flask equipped with a stirrer, thermometer,condenser, drying tube and nitrogen inlet are placed the followingmaterials:______________________________________IngredientsQuantity______________________________________2-acetyl-3,3-dimethyl-norbornane28.5 g (0.17 moles)magnesium 12.0 g (0.5 moles)methallyl chloride 45.27g (0.5 moles)______________________________________

This reaction is carried out under the same conditions as the reactionof Example XXVIII. The work up is carried out by hydrolyzing with NH₄ Clsolution, filtering and separating the layers. After stripping off thesolvent, 34 grams of product remains. The resulting product is thendistilled on a micro Vigreaux column after adding thereto 5 gramsPrimol.sup.® and a trace quantity ofIonox.sup.®.______________________________________NMR Data:δ, ppmInterpretation______________________________________1.27-1.06 methylprotons1.86 CCH₃2.12-1.32 ##STR261##4.74-4.94##STR262##______________________________________

infrared Data:

880, 1080, 1105, 1360, 1380, 1455, 1630, 2860, 2940, 3500 cm⁻¹.

The NMR spectrum is set forth in FIG. 48. The Infrared spectrum is setforth in FIG. 49.

EXAMPLE XXXI PREPARATION OF3,3-DIMETHYL-2-(4-METHYL-4-PENTENOYL)-NORBORNANE

Reaction: ##STR263##

A suspension of 146 g of sodium hydride (55% mineral oil dispersion) in1500 g of toluene is heated to 100° C and a solution of 500 g of2-acetyl-3,3-dimethylnorbornane in 250 g of toluene is added over aperiod of 1 hour. The mixture is stirred at 100-103° C until no furtherhydrogen gas is evolved (total gas evolved=66 liters at 1 atmosphere).

A solution of 280 g of methallyl chloride in 250 g of toluene is thenadded over a period of 1 hour at 100-105° C. The mixture is stirred at100-110° C for an additional 14 hours and then cooled to roomtemperature. The mixture is washed several times with water and thesolvent is recovered at atmospheric pressure. The solvent free materialis distilled rapidly through a short column under reduced pressure, andthe distillate is carefully fractionated using a 12 inch × 1 inchGoodloe packed column to give (i) 214 g of an oil, b.p. 100-111° C/0.9mm Hg, which is shown by GLC profile illustrated in FIG. 50 to be amixture of (A) 3,3-dimethyl-2(4'-methyl-4'-pentenoyl)-norbornane and (B)2-acetyl-2-methallyl-3,3-dimethylnorbornane in the approximate ratio of3:1 and (ii) 78 g of an oil, b.p. 122° C/0.8 mm Hg, which wasessentially pure (C)3,3-dimethyl-2-(2'-methallyl-4'-methyl-4'-pentenoyl)-norbornane.

The NMR data for compound A are set forth below:

    ______________________________________                                        δ, ppm                                                                          Interpretation                                                                              Structure                                               ______________________________________                                        4.70    multiplet                                                                                    ##STR264##                                             1.74    broadened singlet                                                                            ##STR265##                                             1.24 0.86                                                                             singlet                                                                                      ##STR266##                                             ______________________________________                                    

the infrared datum for Compound A is set forth below: 1701 cm.sup. -1

The NMR spectrum for this compound is set forth in FIG. 51. The Infraredspectrum for this compound is set forth in FIG. 52.

The NMR data for Compound B are set forth below:

    ______________________________________                                        δ, ppm                                                                          Interpretation                                                                              Structure                                               ______________________________________                                        4.82 4.67                                                                             broad singlet                                                                                ##STR267##                                             2.09    singlet                                                                                      ##STR268##                                             1.69    broad singlet                                                                                ##STR269##                                             1.10 1.03                                                                             singlet                                                                                      ##STR270##                                             ______________________________________                                    

the Infrared datum for Compound B is set forth below:

1690 cm.sup. -1

The NMR spectrum for this compound is set forth in FIG. 3. The Infraredspectrum for this compound is set forth in FIG. 54.

The NMR anaylsis for Compound C are set forth below:

    ______________________________________                                        δ, ppm                                                                             Interpretation                                                                              Structure                                            ______________________________________                                        4.77       multiplet                                                                                    ##STR271##                                          1.76 1.63  2 broad singlets                                                                             ##STR272##                                          1.22 0.87  2 singlets                                                                                   ##STR273##                                          ______________________________________                                    

the Infrared datum for Compound C is set forth below:

1695 cm⁻¹

The NMR spectrum for this compound is set forth in FIG. 55. The Infraredspectrum for this compound is set forth in FIG. 56.

The mixture of compounds having the structures: ##STR274## from a flavoruse standpoint, at the level of 10 ppm, has a camphoraceous, woody,minty aroma with a strong cooling nuance making it useful in dentrificesand mouthwashes. In tobacco, at the level of 200 ppm, it gives coolingand floral notes on smoking. From a perfumery use standpoint, thismaterial has a fruity, woody note which is surprisingly long lasting.

The compound having the structure: ##STR275## has a low-keyed, sweet,camphoraceous, cedarwoody aroma with green herbal and piney notes, froma perfumery use standpoint.

The compound having the structure: ##STR276## from a perfumery usestandpoint, has a low-keyed, sweet, green woody, herbal aroma.

EXAMPLE XXXII PREPARATION OF A COSMETIC POWDER COMPOSITION

A cosmetic powder is prepared by mixing in a ball mill, 100 g of talcumpowder with 0.25 g of the composition prepared according to Example XV.It has an excellent pine needle aroma with green, melony, herbal, twiggyand cut wood characteristics.

EXAMPLE XXXIII PERFUMED LIQUID DETERGENT

Concentrated liquid detergents (lysine salt of n-dodecyl benzenesulfonic acid as more specifically described in U.S. Pat. No. 3,948,818,issued on Apr. 6, 1976) with intense pine needle aromas are preparedcontaining 0.10%, 0.15% and 0.20% of the perfume composition producedaccording to Example XV. The detergents are prepared by adding andhomogeneously mixing the appropriate quantity of perfume oil compositionof Example XV. The detergents all possess intense pine needle aromas,with green, melony, herbal, twiggy and cut wood characteristics, withthe intensity increasing with greater concentrations of the formulationsof Example XV.

EXAMPLE XXXIV PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME

The composition produced according to Example XV is incorporated into acologne at a concentration of 2.5% in 85% aqueous ethanol. A distinctand definite pine needle fragance with green, melony, herbal, twiggy andcut wood notes is imparted to the cologne. The composition of Example XVis also added to a handkerchief at a concentration of 20% (in 95%aqueous ethanol) and a distinct and definite pine needle fragrance withgreen, melony, herbal, twiggy and cut wood characteristics is impartedto the handkerchief perfume.

EXAMPLE XXXV PREPARATION OF A SOAP COMPOSITION

100 Grams of soap chips are mixed with 1 gram of the perfume compositionof Example XV until a substantially homogeneous composition is obtained.The perfumed soap composition manifests an excellent pine needlefragance with green, melony, herbal, twiggy and cut woodcharacteristics.

EXAMPLE XXXVI PREPARATION OF A COSMETIC POWDER COMPOSITION

A cosmetic powder is prepared by mixing in a ball mill, 100 g of talcumpowder with 0.25 g of the composition prepared according to Example XII.It has an excellent pine needle aroma with sweet, woody, fruity, spicey(nutmeg, pepper), and herbaceous characteristics.

EXAMPLE XXXVII PERFUMED LIQUID DETERGENT

Concentrated liquid detergents (lysine salt of n-dodecyl benzenesulfonic acid as more specifically described in U.S. Pat. No. 3,948,818,issued on Apr. 6, 1976) with intense pine needle aromas are preparedcontaining 0.10%, 0.15% and 0.20% of the perfume composition producedaccording to Example XII. The detergents are prepared by adding andhomogeneously mixing the appropriate quantity of perfume oil compositionof Example XII. The detergents all possess intense pine needle aromas,with sweet, woody, fruity, spicey (nutmeg, pepper), and herbaceouscharacteristics, with the intensity increasing with greaterconcentrations of the formulations of Example XII.

EXAMPLE XXXVIII PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME

The composition produced according to Example XII is incorporated into acologne at a concentration of 2.5% in 85% aqueous ethanol. A distinctand definite pine needle fragrance with sweet, woody, fruity, spicey,(nutmeg, pepper), and herbaceous characteristics is imparted to thecologne. The composition of Example XII is also added to a handkerchiefat a concentration of 20% (in 95% aqueous ethanol) and a distinct anddefinite pine needle fragrance with sweet, woody, fruity, spicey(nutmeg, pepper), and herbaceous characteristics is imparted to thehandkerchief perfume.

EXAMPLE XXXIX PREPARATION OF A SOAP COMPOSITION

100 Grams of soap chips are mixed with 1 gram of the perfume compositionof Example XII until a substantially homogeneous composition isobtained. The perfumed soap composition manifests an excellent pineneedle fragrance with sweet, woody, fruity, spicey (nutmeg, pepper), andherbaceous characteristics.

EXAMPLE XL PREPARATION OF A COSMETIC POWDER COMPOSITION

A cosmetic powder is prepared by mixing in a ball mill, 100 g of talcumpowder with 0.25 g of the composition prepared according to Example III.It has an excellent pine needle aroma with fruity, herbaceous, armoisand fir-balsam characteristics.

EXAMPLE XLI PERFUMED LIQUID DETERGENT

Concentrated liquid detergents (lysine salt of n-dodecyl benzenesulfonic acid as more specifically described in U.S. Pat. No. 3,948,818,issued on Apr. 6, 1976) with intense pine needle aromas are preparedcontaining 0.10%, 0.15% and 0.20% of the perfume composition producedaccording to Example III. The detergents are prepared by adding andhomogeneously mixing the appropriate quantity of the perfume oilcomposition of Example III. The detergents all possess intense pineneedle aromas, with fruity, herbaceous, armois and fir-balsamcharacteristics, with the intensity increasing with greaterconcentrations of the formulations of Example III.

EXAMPLE XLII PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME

The composition produced acording to Example III is incorporated into acologne at a concentration of 2.5% in 85% aqueous ethanol. A distinctand definite pine needle fragrance with fruity, herbaceous, armois andfir-balsam characteristics is imparted ot the cologne. The compositionof Example III is also added to a handkerchief at a concentration of 20%(in 95% aqueous ethanol) and a distinct and definite pine needlefragrance with fruity, herbaceous, armois and fir-balsam characteristicsis imparted to the handkerchief perfume.

EXAMPLE XLIII PREPARATION OF A SOAP COMPOSITION

100 Grams of soap chips are mixed with 1 gram of the perfume compositionof Example III until a substantially homogeneous composition isobtained. The perfumed soap composition manifests an excellent pineneedle fragrance with fruity, herbaceous, armois and fir-balsamcharacteristics.

EXAMPLE XLIV PREPARATION OF A COSMETIC POWDER COMPOSITION

A cosmetic powder is prepared by mixing in a ball mill, 100 g of talcumpowder with 0.25 g of the composition prepared according to Example II.It has an excellent pine needle aroma with sweet, woody, thujone-like,armoise, cedarleaf and camphoraceous characteristics.

EXAMPLE XLV PERFUMED LIQUID DETERGENT

Concentrated liquid detergents (lysine salt of n-dodecyl benzenesulfonic acid as more specifically described in U.S. Pat. No. 3,948,818,issued on Apr. 6, 1976) with intense pine needle aromas are preparedcontaining 0.10%, 0.15% and 0.20% of the perfume composition producedaccording to Example II. The detergents are prepared by adding andhomogeneously mixing the appropriate quantity of the perfume oilcomposition of Example II. The detergents all possess intense pineneedle aromas, with sweet, woody, thujone-like, armoise, cedar-leaf andcamphoraceous characteristics, with the intensity increasing withgreater concentrations of the formulations of Example II.

EXAMPLE XLVI PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME

The composition produced according to Example II is incorporated into acologne at a concentration of 2.5% in 85% aqueous ethanol. A distinctand definite pine needle fragrance with sweet, woody, thujone-like,armoise, cedar-leaf and camphoraceous characteristics is imparted to thecologne. The composition of Example II is also added to a handkerchiefat a concentration of 20% (in 95% aqueous ethanol) and a distinct anddefinite pine needle fragrance with sweet, woody, thujone-like, armoise,cedar-leaf and camphoraceous characteristics is imparted to thehandkerchief perfume.

EXAMPLE XLVII PREPARATION OF A SOAP COMPOSITION

100 Grams of soap chips are mixed with 1 gram of the perfume compositionof Example II until a substantially homogenous composition is obtained.The perfumed soap composition manifests an excellent pine needlefragrance with sweet, woody, thujone-like, armoise, cedar-leaf andcamphoraceous characteristics.

EXAMPLE XLIX PERFUMED LIQUID DETERGENT

Concentrated liquid detergents (lysine salt of n-docedyl benzenesulfonic acid as more specifically described in U.S. Pat. No. 3,948,818,issued on Apr. 6, 1976) with intense pine needle aromas are preparedcontaining 0.10%, 0.15% and 0.20% of the perfume composition producedaccording to Example XIX. The detergents are prepared by adding andhomogeneously mixing the appropriate quantity of the perfume oilcomposition of Example XIX. The detergents all possess intense pineneedle aromas, with fruity, musty, sweet, woody, minty nuances withfresh cut pine/spruce characteristics, with the intensity increasingwith greater concentrations of the formulations of Example XIX.

EXAMPLE L PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME

The composition produced accordng to Example XIX is incorporated into acologne at a concentration of 2.5% in 85% aqueous ethanol. A distinctand definite pine needle fragrance with fruity, musty, sweet, woody,minty, fresh cut pine/spruce notes is imparted to the cologne. Thecomposition of Example XIX is also added to a handkerchief at aconcentration of 20% (in 95% aqueous ethanol) and a distinct anddefinite pine needle fragrance with fruity, musty, sweet, woody, minity,fresh cut pine/spruce characteristics is imparted to the handkerchifeperfume.

EXAMPLE LI PREPARATION OF A SOAP COMPOSITION

100 Grams of soap chips are mixed with 1 gram of the perfume compositionof Example XIX until a substantially homogeneous composition isobtained. The perfumed soap composition manifests an excellent pineneedle fragrance with fruity, musty, sweet, woody, minty and fresh cutpine/spruce characteristics.

EXAMPLE LII PREPARATION OF A COSMETIC POWDER COMPOSITION

A cosmetic powder is prepared by mixing in a ball mill, 100 g of talcumpowder with 0.25 g of the composition prepared according to ExampleXVII. It has an excellent pine needle aroma with musty, sweet fruity,woody and artemesia characteristics.

EXAMPLE LIII PERFUMED LIQUID DETERGENT

Concentrated liquid detergents (lysine salt of n-dodecyl benzenesulfonic acid as more specifically described in U.S. Pat. No. 3,948,818,issued on Apr. 6, 1976) with intense pine needle aromas are preparedcontaining 0.10%, 0.15% and 0.20% of the perfume composition producedaccording to Example XVII. The detergents are prepared by adding andhomogeneously mixing the appropriate quantity of the perfume oilcomposition of Example XVII. The detergents all possess intense pineneedle aromas, with musty, sweet fruity, woody and artemesiacharacteristics, with the intensity increasing with greaterconcentrations of the formulations of Example XVII.

EXAMPLE LIV PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME

The composition produced according to Example XVII is incorporated intoa cologne at a concentration of 2.5% in 85% aqueous ethanol. A distinctand definite pine needle fragrance with musty, sweet fruity, woody andartemesia notes is imparted to the cologne. The composition of ExampleXVII is also added to a handkerchief at a concentration of 20% (in 95%aqueous ethanol) and a distinct and definite pine needle fragrance withmusty, sweet fruity, woody and artemesia characteristics is imparted tothe handkerchief perfume.

EXAMPLE LV PREPARATION OF A SOAP COMPOSITION

100 Grams of soap chips are mixed with 1 gram of the perfume compositionof Example XVII until a substantially homogeneous composition isobtained. The perfumed soap composition manifests an excellent pineneedle fragrance with musty, sweet fruity, woody and artemesiacharacteristics.

EXAMPLE LVI PREPARATION OF A COSMETIC POWER COMPOSITION

A cosmetic powder is prepared by mixing in a ball mill, 100 g of talcumpowder with 0.25 g of the composition prepared according to Example XI.It has an excellent pine needle aroma with woody, piney, natural-likenuances with fruity, spicey, cresylic, borneol characteristics with adefinitive berry top note.

EXAMPLE LVII PERFUMED LIQUID DETERGENT

Concentrated liquid detergents (lysine salt of n-dodecyl benzenesulfonic acid as more specifically described in U.S. Pat. No. 3,948,818,issued on Apr. 6, 1976) with intense pine needle aromas are preparedcontaining 0.10%, 0.15% and 0.20% of the perfume composition producedaccording to Example XI. The detergents are prepared by adding andhomogeneously mixing the appropriate quantity of the perfume oilcomposition of Example XI. The detergents all possess intense pineneedle aromas, with woody, piney, natural-like nuances with fruity,spicey, cresylic, borneol characteristics with a definitive berry topnote, with the intensity increasing with greater concentrations of theformulations of Example XI.

EXAMPLE LVIII PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME

The composition produced according to Example XI is incorporated into acologne at a concentration of 2.5% in 85% aqueous ethanol. A distinctand definite pine needle fragrance with woody, piney, natural-likenuances with fruity, spicey, cresylic, borneol characteristics with adefinitive berry top note is imparted to the cologne. The composition ofExample XI is also added to a handkerchief at a concentration of 20% (in95% aqueous ethanol) and a distinct and definite pine needle fragrancewith woody, piney, natural-like nuances with fruity, spicey, cresylic,borneol characteristics with a definitive berry top note is imparted tothe handkerchief perfume.

EXAMPLE LIX PREPARATION OF A SOAP COMPOSITION

100 Grams of soap chips are mixed with 1 gram of the perfume compositionof Example XI until a substantially homogenous composition is obtained.The perfumed soap composition manifests an excellent pine needlefragrance with woody, piney, natural-like nuances with fruity, spicey,cresylic, borneol characteristics with a definitive berry top note.

EXAMPLE LX TOBACCO FILTER

Into a 20 mm cellulose acetate filter is added:

alpha-ethyl-3,3-dimethyl-2-norbornanemethanol at the rate of 1,000 ppm(10 micro liter of a 10% solution of said filter)

The filter is then attached to a full flavor cigarette on the market,e.g. (1) Marlboro.sup.®, (2) Winston.sup.® or (3) Viceroy.sup.®, as wellas on a Kentucky 1A3 reference cigarette (produced by the University ofKentucky), yielding the following results:

1. Both cigarettes containing said norbornanemethanol additive, whencompared to a cigarette having a filter without said norbornanemethanoladditive, give rise to sweet, woody, piney aromas on smoking, with apleasant, cooling effect and rather noticeable reduced harshness.

2. Both cigarettes containing said norbornanemethanol additive have alesser degree of "hotness" and give rise to a "fresh" taste on smoking.

(1) registered trademark of the Phillip Morris Company.

(2) Registered trademark of the R. J. Reynolds Company.

(3) Registered trademark of the Brown & Williamson Company.

EXAMPLE LXI SODIUM BOROHYDRIDE REDUCTION OF2-(2-BUTENOYL)-3,3-DIMETHYLNORBORNANE

Reaction: ##STR277##

Into a 500 cc three necked reaction flask equipped with a stirrer,condenser and thermometer is placed 82 g (43 moles) of a materialcontaining more than 90% 2-(trans-2-butenoyl)-3,3-dimethylnorbornane(produced according to Example XII) and 250 g of anhydrous methanol.Over a period of 1 hour, 7 g of sodium borohydride is added to thereaction mass, while the reaction mass remains at 25-26° C.

The reaction mass is then stirred for a period of 3 hours at 25-28° C,whereupon another 7 grams of sodium borohydride is added. The reactionmass is then stirred for another 3 hours until no further change in theGLC profile is observed. The resulting mixture is then transferred to a1 liter flask, and the methanol is stripped off leaving a slurry. To theslurry is added 500 ml water, and the resulting mixture is extractedwith 150 ml of cyclohexane. The cyclohexane extract is stripped anddistilled rapidly at 100-115° C and a vacuum of 2.4-2.6 mm Hg. Afteradding to the resulting material 5 g Primol.sup.® and 0.1 g ofIonol.sup.®, the rushed over material is fractionally distilled on a 8plate Vigreux column at 113-120° C vapor temperature and 2.7-4.4 mm Hgpressure (reflux ratio 20:1). Ten fractions are produced of whichfractions 2-8 are used for flavor and perfumery work.

The resulting material is primarily a mixture of three compounds havingthe structures: ##STR278## as confirmed by NMR, IR and Mass Spectralanalyses.

The resulting mixture is evaluated at 10% in food grade ethanol, from aperfumery standpoint, and has sweet piney, bornyl acetate-like, berryand somewhat woody notes.

From a flavor standpoint, it has a spicey, valerian oil-like,calamus-like, pine needle-like, herbaceous and fruity aroma characterwith a valerian oil-like, calamus, pine needle, herbaceous and fruityflavor character at 1 ppm.

The resulting mixture has uses in spce flavors, cordial flavors, pineneedle flavors and root beer flavors.

The GC-MS profile for the compound having the structure: ##STR279## isset forth in FIG. 57.

The GC-MS profile for the compound having the structure: ##STR280## isset forth in FIG. 58.

The GC-MS profile for the compound having the structure: ##STR281## isset forth in FIG. 59.

The GC-MS profile for the mixture of remaining compounds in the reactionproduct is set forth in FIG. 60.

What is claimed is:
 1. A process for preparing a norbornane derivativewhich comprises the steps of (i) reacting2-acetyl-3,3-dimethyl-5-norbornene with a compound having the structure:##STR282## wherein X is selected from the group consisting of chlorine,bromine or iodine thereby forming a first organometallic compound havingthe structure: ##STR283## (ii) admixing the first organometalliccompound thus formed with acetaldehyde thereby forming a secondorganometallic compound having the structure: ##STR284## (iii)hydrolyzing said second organometallic compound to form a keto alcoholhaving the structure: ##STR285## (iv) reacting said keto alcohol with amixture of either an alkanoic metal acetate and acetic anhydride orparatoluenesulfonic acid in benzene or toluene thereby formingendo-2-(2'-butenoyl)-3,3-dimethyl-5-norbornene having the structure:##STR286##